Polyolefin production with chromium-based catalysts

ABSTRACT

A method including contacting a chromium-based catalyst with a reducing agent in a solvent to lower an oxidation state of at least some chromium in the chromium-based catalyst to give a reduced chromium-based catalyst, drying the reduced chromium-based catalyst at a temperature, and adjusting the temperature to affect the flow index response of the reduced chromium-based catalyst.

FIELD OF THE INVENTION

The present invention relates generally to polyolefin production withchromium-based catalysts and, more particularly, to preparing andreducing the chromium-based catalysts for the polymerization of olefininto a polyolefin in a polymerization reactor.

DESCRIPTION OF THE RELATED ART

Polyolefins have been used extensively in a wide variety of applicationsinclusive of food packaging, textiles, and resin materials for variousmolded articles. Different polymer properties may be desired dependingon the intended use of the polymer. For example, polyolefins havingrelatively low molecular weights and narrow molecular weightdistributions are suitable for articles molded by an injection moldingmethod. On the other hand, polyolefins having relatively high molecularweights and broad molecular weight distributions are suitable forarticles molded by blow molding or inflation molding. For example, inmany applications, medium-to-high molecular weight polyethylenes aredesirable. Such polyethylenes have sufficient strength for applicationswhich require such strength (e.g., pipe applications), andsimultaneously possess good processing characteristics. Similarly,polyolefins having a particular flow index or within a particular flowindex range are suitable for various applications.

Ethylene polymers having broad molecular weight distributions can beobtained by use of a chromium-based catalyst obtained by calcining achromium compound carried on an inorganic oxide carrier in anon-reducing atmosphere to activate it such that, for example, at leasta portion of the carried chromium atoms is converted to hexavalentchromium atoms (Cr+6). This type of catalyst is commonly referred to inthe art as the Phillips catalyst. The chromium compound is impregnatedonto silica, dried to a free-flowing solid, and heated in the presenceof oxygen to about 400° C.-860° C., converting most or all of thechromium from the +3 to the +6 oxidation state.

Another chromium-based catalyst used for high density polyethyleneapplications consists of silyl chromate (e.g., bis-triphenylsilylchromate) chemisorbed on dehydrated silica and subsequently reduced withdiethylaluminum ethoxide (DEAlE). The resulting polyethylenes producedby each of these catalysts are different with respect to some importantproperties. Chromium oxide-on-silica catalysts have good productivity (gPE/g catalyst), also measured by activity (g PE/g catalyst-hr), butoften produce polyethylenes with molecular weight distributions narrowerthan that desired for applications such as large part blow molding,film, and pressure pipe. Silyl chromate-based catalysts producepolyethylenes with desirable molecular weight characteristics (broadermolecular weight distribution with a high molecular weight shoulder onmolecular weight distribution curve), but often may not have as highproductivity or activity as chromium oxide-on-silica catalysts.

Monoi et al., in Japanese Patent Application 2002-020412, disclose theuse of inorganic oxide-supported Cr+6-containing solid components (A)prepared by activating under non-reducing conditions, then addingdialkylaluminum functional group-containing alkoxides (B) which containan Al—O—C—X functional group in which X is either an oxygen or anitrogen atom, and trialkylaluminum (C) to polymerize ethylene. Theresulting ethylene polymers are said to possess good environmentalstress crack resistance and good blow molding creep resistance.

Monoi et al., in U.S. Pat. No. 6,326,443, disclose the preparation of apolyethylene polymerization catalyst using a chromium compound, addingan organic aluminum compound more rapidly than specified by a certainmathematical formula, and drying the resulting product at a temperaturenot higher than 60° C., more rapidly than specified by anothermathematical formula. Both formulae are expressed as functions of batchsize. Monoi teaches that by minimizing the addition time of the organicaluminum compound and the drying time, a catalyst with high activity andgood hydrogen response is obtained.

Monoi et al., in U.S. Pat. No. 6,646,069, disclose a method of ethylenepolymerization in co-presence of hydrogen using a trialkylaluminumcompound-carried chromium-based catalyst, wherein the chromium-basedcatalyst is obtained by activating a chromium compound carried on aninorganic oxide carrier by calcination in a non-reducing atmosphere toconvert chromium atoms into the +6 state, treating the resultingsubstance with a trialkylaluminum compound in an inert hydrocarbonsolvent, and then removing the solvent.

Hasebe et al., in Japanese Patent Publication 2001-294612, disclosecatalysts containing inorganic oxide-supported chromium compoundscalcined at 300° C.-1100° C. in a non-reducing atmosphere, R3-nAlLn(R=C1-C8 alkyl; L=C1-C8 alkoxy or phenoxy; and 0<n<1), and Lewis baseorganic compounds. The catalysts are said to produce polyolefins withhigh molecular weight and narrow molecular weight distribution.

Da et al, in Chinese Patent 1214344, teach a supported chromium-basedcatalyst for gas-phase polymerization of ethylene prepared byimpregnating an inorganic oxide support having hydroxyl group on thesurface with an inorganic chromium compound aqueous solution. Theparticles formed are dried in air and activated in an oxygen-containingatmosphere. The activated catalyst intermediate is reduced with anorganic aluminum compound.

Durand et al., in U.S. Pat. No. 5,075,395, teach a process forelimination of the induction period in the polymerization of ethylene.The polymerization is conducted with a charge powder in the presence ofa catalyst comprising a chromium oxide compound associated with agranular support and activated by thermal treatment, this catalyst beingused in the form of a prepolymer. The Durand process is characterized inthat the charge powder employed is previously subjected to a treatmentby contacting the charge powder with an organoaluminum compound in sucha way that the polymerization starts up immediately after the contactingof the ethylene with the charge powder in the presence of theprepolymer.

The above described chromium-based catalysts may be used to produceselect grades of polymers. Very often, polymerization reactors arerequired to produce a broad range of products, having flow indices thatmay vary from 0.1 dg/min to about 100 dg/min, for example. The flowindex response of a chromium-based catalyst refers to the range of theflow index of the polymer made by the catalyst under a given set ofpolymerization conditions.

SUMMARY

An embodiment relates to a method of preparing a chromium-based catalystfor the polymerization of an olefin into a polyolefin, the methodincluding: contacting a chromium-based catalyst with a reducing agent ina solvent to lower an oxidation state of at least some chromium in thechromium-based catalyst to give a reduced chromium-based catalyst;drying the reduced chromium-based catalyst at a drying line-outtemperature; and adjusting the drying line-out temperature to change theflow index response of the reduced chromium-based catalyst.

Another embodiment relates to a method of preparing a chromium-basedcatalyst for the production of polyolefin, the method including:contacting a chromium-based catalyst with a reducing agent in thepresence of a solvent in a mix vessel to produce a reducedchromium-based catalyst; evaporating the solvent at a drying temperatureto dry the reduced chromium-based catalyst; and specifying the dryingtemperature to give a desired flow index response of the reducedchromium-based catalyst.

Yet another embodiment relates to a method including preparing achromium oxide catalyst for the polymerization of an olefin into apolyolefin, the preparing involving: mixing the chromium oxide catalystwith a reducing agent in a solvent to give a reduced chromium oxidecatalyst; removing solvent from the reduced chromium oxide catalyst at aspecified temperature set point; and adjusting the specified temperatureset point to give a desired flow index response of the reduced chromiumoxide catalyst. The method includes collecting the reduced chromiumoxide catalyst for delivery to a polyolefin polymerization reactor.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a block flow diagram of a reducing system for chromium-basedcatalyst in accordance with embodiments of the present techniques.

FIG. 2 is a simplified process flow diagram of the reducing system ofFIG. 1 in accordance with embodiments of the present techniques.

FIG. 3A is a diagrammatical representation of a conduit extension for amix vessel of a chromium-based catalyst reducing system in accordancewith embodiments of the present techniques.

FIG. 3B is a diagrammatical representation of an entrance arrangementemploying the conduit extension of FIG. 3A in accordance withembodiments of the present techniques.

FIG. 4 is a bar chart of exemplary flow index in a laboratoryslurry-phase polymerization reactor as a function of entrancearrangement for reducing agent to an upstream pilot-plant catalyst mixvessel in accordance with embodiments of the present techniques.

FIG. 5 is a bar chart of exemplary flow index in a pilot-plant gas-phasereactor as a function of entrance arrangement for reducing agent to anupstream pilot-plant catalyst mix vessel in accordance with embodimentsof the present techniques.

FIG. 6 is a plot of a fitted curve of example data of flow index in alaboratory slurry-phase polymerization reactor as a function of catalystdrying temperature in an upstream pilot-plant catalyst mix vessel inaccordance with embodiments of the present techniques.

FIG. 7 is a plot of a fitted curve of example data of flow index in apilot-plant gas-phase reactor as a function of catalyst dryingtemperature in an upstream pilot-plant catalyst mix vessel in accordancewith embodiments of the present techniques.

FIG. 8 is a block diagram of a method of preparing a chromium-basedcatalyst including adjusting catalyst drying temperature for thepolymerization of an olefin into a polyolefin in accordance withembodiments of the present techniques.

FIG. 9 is a block diagram of a method of preparing a chromium-basedcatalyst for polyolefin production, the method including introducing areducing agent through an entrance arrangement on a mix vessel havingthe chromium-based catalyst in accordance with embodiments of thepresent techniques.

FIG. 10 is block flow diagram of a polymerization reactor system havingan inline reduction system for mixing a reducing agent with asubstantially continuous feed of chromium-based catalyst in accordancewith embodiments of the present techniques.

FIG. 11 is a block diagram of a method of operating a polyolefin reactorsystem, including feeding a chromium-based catalyst through an inlinereduction system to a polymerization reactor in accordance withembodiments of the present techniques.

DETAILED DESCRIPTION

Before the present compounds, components, compositions, and/or methodsare disclosed and described, it is to be understood that unlessotherwise indicated this invention is not limited to specific compounds,components, compositions, reactants, reaction conditions, ligands,catalyst structures, or the like, as such may vary, unless otherwisespecified. It is also to be understood that the terminology used hereinis for the purpose of describing particular embodiments only and is notintended to be limiting.

As discussed below, embodiments of the present techniques include toadjust drying temperature of a reduced chromium-based catalyst in a mixvessel to give a desired flow index response of the catalyst. Also, anentrance arrangement on the mix vessel may be employed to direct flow ofthe reducing agent into the mix vessel to improve dispersion of thereducing agent and to increase the flow index response prior to dryingof the catalyst. Further, some embodiments may use an inline mixer inlieu of the mix vessel, for the inline reduction of the chromium-basedcatalyst in route to the polyolefin polymerization reactor.

Embodiments of the techniques may be directed to controlling andadjusting flow index response. The techniques may facilitate increasingand decreasing the flow index response beyond the typical process rangeof a given chromium-based catalyst. Embodiments provide for adjustingthe catalyst flow index response in the production of chromium-basedcatalysts for use in the polymerization of olefin into polyolefin. Inother words, the chromium-based catalyst compositions may be used in thepolymerization of olefins, wherein the chromium-based catalystcomposition has a flow index response within a selected or desiredrange. Further, techniques herein may also beneficially maintain orincrease productivity of the catalyst.

Generally, embodiments disclosed herein relate to controlling ortailoring the flow index response of supported chromium-based catalysts.In the production of the chromium-based catalyst, the catalyst may becontacted with a reducing agent at an adjustable feed rate of reducingagent over an adjustable time period and with adjustable agitation rate,and then drying the catalyst at an adjustable drying temperature (anddrying time) to give a reduced chromium-based catalyst having a flowindex response within a desired range. These reduced chromium-basedcatalysts may then be employed to polymerize olefins into polyolefinshaving a flow index correlative to the flow index response. Indeed, acatalyst with higher flow index response generally gives a polyolefinwith higher flow index, and a catalyst with lower flow index responsegenerally gives a polyolefin with lower flow index.

In the reduction of the catalyst prior to polymerization, the additionrate of a reducing agent (e.g., DEAlE) to a chromium-based catalyst(e.g., silyl chromate or chromium oxide catalysts), and the agitationrate of the reduction reaction mixture influences the flow indexresponse of the catalyst. As discussed below in accordance withembodiments of the present techniques, the flow index response of thecatalyst can further be controlled or adjusted by adjusting the dryingtemperature of the catalyst after the reduction reaction, such as inplace in the mix vessel that held the reduction reaction. As usedherein, “flow index response” means that under a certain set ofpolymerization reaction conditions, the catalyst produces a polymerwithin a certain molecular weight range.

In the subsequent polymerization with the catalyst, the molar ratio ofDEAlE/Cr in the catalyst or the weight percent (wt %) DEAlE in thecatalyst, polymerization temperature, residence time of the catalyst inthe polymerization reactor, trace oxygen add-back concentrationintroduced to or present in the reactor, and comonomer and hydrogenratios to ethylene may each affect the molecular weight of the polymermade with the catalyst. When the catalyst is prepared consistently, andthe subsequent polymerization process variables are held constant orgenerally constant, a catalyst of a certain formulation should make thesame polymer. Even with minor variations in the preparation and processvariables, such as within a given control tolerance, a similar polymershould be formed. Thus, control of the flow index response of a catalystin the production of the catalyst may be implemented to give a certainmolecular weight range for the polymer in the downstream polymerizationaccording to embodiments disclosed herein.

Polymer flow index is inversely related to polymer molecular weight. Theflow index response may be modified herein using terms such as “high,”“medium,” or “low” to indicate the relative range of the flow index ofthe resulting polymer made under a given set of polymerizationconditions as compared to similar chromium-based catalyst compositionsproduced using varying reducing agent feed rates, time periods foraddition of the reducing agent, reducing agent entrance arrangements,agitation rates, and/or drying temperature or drying line-outtemperature. For example, for a given chromium-based catalystcomposition produced using two different selected DEAlE feed rates overa given time period, one catalyst may have a low flow index response,producing a higher molecular weight polymer, while the other may have ahigh flow index response, producing a lower molecular weight polymer.These relative terms should generally not be used to compare differentchromium-based catalysts, but may be used to differentiate the flowindex response for a given chromium-based catalyst.

Polymer melt index is another indicator of polymer molecular weight.Melt index is a measure of the polymer fluidity and is also inverselyrelated to molecular weight. A higher melt index can indicate a highertermination of active polymer chains relative to propagation, and, thus,a lower molecular weight.

As discussed in Moorhouse et al., U.S. Pat. Publication No.2011/0010938, which is incorporated herein by reference in its entirety,the present inventors found that reducing agent feed rate, in someexamples, or that reducing agent feed rate and agitation rate, in otherexamples, during addition of and reaction of the reducing agent with thecatalyst may impact the flow index response of the catalysts. It may bebeneficial to maintain control over these parameters to produce batchesof catalyst with a consistent or desired flow index response.Furthermore, in accordance with embodiments of the present techniques,the drying temperature (and in some cases, the drying time) of thecatalyst may be adjusted to give a desired flow index response of thecatalyst. Accordingly, the flow index response may be beneficiallyvaried to produce catalysts for production of polyethylene for differentapplications by adjusting or selecting reducing agent addition rates andagitation rates, and the drying temperature of the catalyst.

For a selected or specified reducing agent/Cr ratio, the flow indexresponse of a chromium-based catalyst may be affected by the addition ofthe reducing agent, including the feed rate and the time period overwhich the reducing agent is added. For example, the flow index responsegenerally increases with a slower rate of addition of the reducingagent. Also, the flow index response generally increases with a fasterrate of agitation during addition and reaction of the reducing agent, ora combination of slower rate of addition and faster rate of agitation.Consequently, in applications where the desired flow index response islow, the reducing agent may be added at a high feed rate over a shorttime period or the agitation rate decreased. Conversely, forapplications where the desired flow index response is high, the reducingagent may be added at a lower feed rate over a longer period of time orthe agitation rate increased.

Furthermore, in accordance with embodiments of the present techniques,the flow index response of a chromium-based catalyst may be affected byadjusting the catalyst drying temperature (and drying time). Forexample, the flow index response has been found to increase with areduced drying temperature. Consequently, in applications where a higherflow index response is desired, the drying temperature may be lowered(e.g., such as from 80° C. to 60° C. in one example). Conversely, forapplications where a low flow index response is desired, the dryingtemperature may be raised. It has also been found that lowering thecatalyst drying temperature may also increase productivity of thecatalyst in the downstream polymerization. Catalyst productivity is theratio of mass of polyolefin (e.g., polyethylene) produced per mass ofcatalyst used in the polymerization, i.e., in the downstreampolymerization reactor. In cases where the drying temperature is loweredit may be beneficial to lengthen the drying time slightly to achieve thesame low residual solvent level. For instance, at a drying temperatureof 70° C., the drying time may be 18 hours in one example, but if thedrying temperature is lowered to 60° C., then the drying time may be 21hours in that example to reach the same residual solvent level. Ofcourse, other drying temperatures, drying times, and pairs of thesedrying temperatures and times are applicable.

Although embodiments disclosed herein include chromium oxide and silylchromate catalysts, the scope of the disclosure should not be limitedthereby. One of skill in the art would appreciate that the addition ofthe reducing agent could be tailored to produce a desired flow indexresponse of other chromium-based catalysts.

Catalysts useful in embodiments disclosed herein include chromium-basedcatalysts, such as chromium oxide and silyl chromate-based catalysts.The catalyst system chosen for the polymerization often dictates polymerproperties such as molecular weight, molecular weight distribution, andflow index.

Chromium oxide-based catalysts, for example, Phillips-type catalysts,may be formed by impregnating a Cr+3 species into silica, followed bycalcination of the silica support under oxidizing conditions at about300° C. to 900° C., and at about 400° C. to 860° C. in otherembodiments. Under these conditions, at least some of the Cr+3 isconverted to Cr+6. The Phillips catalyst is also commonly referred to inthe prior art as inorganic oxide-supported Cr+6.

Silyl chromate catalysts are another type of inorganic oxide-supportedCr+6 catalysts which tend to produce polyethylenes with improvedproperties for a number of applications. The silyl chromate catalyst maybe formed by dehydrating silica at about 400° C. to 850° C. in air ornitrogen, followed by contacting for specified time a silyl chromatecompound, such as bis(triphenylsilyl) chromate, with the silica slurriedin inert hydrocarbon solvent, then reacting the resulting product withan alkyl aluminum alkoxide, such as diethylaluminum ethoxide (DEAlE),for example, and then drying the resulting catalyst product to removethe solvent therefrom.

Cann et al., in U.S. Publication No 2005/0272886, teaches the use ofaluminum alkyl activators and co-catalysts to improve the performance ofchromium-based catalysts. The addition of aluminum alkyls allow forvariable control of side branching, and desirable productivities, andthese compounds may be applied to the catalyst directly or addedseparately to the reactor. Adding the aluminum alkyl compound directlyto the polymerization reactor (in-situ) eliminates induction times.

Advantageously, by adjusting the addition of a reducing agent (includingthe feed rate and the time period over which the reducing agent isadded), such as DEAlE, to the chromium-based catalyst, and optionallythe agitation rate, flow index response may be tailored. In accordancewith embodiments of the present techniques, the flow index response maybe further tailored by adjusting the drying temperature of the catalyst.

As described herein, flow index is typically an important parameter forpolyolefins applications. The flow index is a measure of the ease offlow of the melt of a thermoplastic polymer. Flow index, or I21, as usedherein is defined as the weight of polymer in grams flowing in 10minutes through a capillary of specific diameter and length by apressure applied via a 21.6 kg load at 190° C. and is usually measuredaccording to ASTM D-1238. The indexes I2 and I5 are similarly defined,where the pressure applied is by a load of 2.16 kg or 5 kg,respectively. I2 and I5 are also referred to as melt indexes.

The flow index is therefore a measure of the ability of a fluid to flowunder pressure and temperature. Flow index is an indirect measure ofmolecular weight, with high flow index corresponding to low molecularweight. At the same time, flow index is inversely proportional to theviscosity of the melt at the conditions of the test, and ratios betweena flow index value and a melt index value such as the ratio of I21 to I2for one material, are often used as a measure for the broadness of amolecular weight distribution.

Flow index is, thus, a very important parameter for polyolefins.Different flow indices may be desirable for different applications. Forapplications such as lubricants, injection molding, and thin films, ahigher flow index polyolefin may be desired, while for applications suchas pipe, large drums, pails or automobile gasoline tanks, a lower flowindex polyolefin may be desired. Polyolefins for a given applicationshould therefore have a flow index sufficiently high to easily form thepolymer in the molten state into the article intended, but alsosufficiently low so that the mechanical strength of the final articlewill be adequate for its intended use.

Reactor process variables may be adjusted to obtain the desired polymerflow index and melt index when using prior art chromium-based catalystsfor which the flow index response was not tailored as according toembodiments disclosed herein. For example, increasing the temperature ofpolymerization is known to enhance the rate of termination, but have acomparatively minor effect on the rate of propagation, as reported in M.P. McDaniel, Advances in Catalysis, Vol. 33 (1985), pp 47-98. This mayresult in more short chain polymers and an increase in melt index andflow index. Catalysts having a low flow index response therefore oftenrequire higher reactor temperatures, higher oxygen add-back, and higherhydrogen concentrations to produce a polymer of a given flow index.

However, there are limits on the range over which reactor processvariables may be adjusted, such as, for example, reactor temperature,hydrogen and oxygen levels, without adversely affecting thepolymerization process or the catalyst productivity. For example,excessively high reactor temperatures may approach the softening ormelting point of the formed polymer. This may then result in polymeragglomeration and reactor fouling. Alternatively, low reactortemperatures may lead to a smaller temperature differential with respectto the cooling water, less efficient heat removal, and ultimatelylowered production capacity. Further, high oxygen add-backconcentrations may lead to reduced catalyst productivity, smalleraverage polymer particle size, and higher fines which may contribute toreactor fouling. Additionally, variations in hydrogen concentrations mayimpact polymer properties such as, for example, die swell which may inturn affect the suitability of a polymer for its desired application.Accordingly, adjusting reactor variables to approach operational limitsmay result in operational problems which may lead to premature reactorshutdown and downtime due to extensive clean-up procedures, as well asundesired gels and other undesired properties of the resulting polymerproduct.

The ability to tailor catalyst flow index response by adjusting the feedrate and/or time period for addition of the reducing agents alone or incombination with adjusting the agitation rate during reducing agentaddition and reaction, as well as adjusting the catalyst dryingtemperature and time, may therefore avoid operational difficulties,reactor shutdowns, and less economical polymerization conditions. Thisability to tailor catalyst flow index response may facilitate productionof catalysts that give polymers with the desired properties to be moreeasily made. Indeed, embodiments of the techniques described hereinrelated to increasing dispersion or mixing of the reducing agent withcatalyst in a reduction mix vessel, adjusting catalyst dryingtemperature in the mix vessel, and the alternative of inline reductionof catalyst, may improve control of flow index in viable operatingregimes.

The chromium-based catalyst compositions disclosed herein may includechromium-based catalysts and reducing agents. The chromium-basedcatalysts used in embodiments of the present disclosure may includechromium oxide catalysts, silyl chromate catalysts, or a combination ofboth chromium oxide and silyl chromate catalysts.

The chromium compounds used to prepare chromium oxide catalysts mayinclude CrO3 or any compound convertible to CrO3 under the activationconditions employed. Many compounds convertible to CrO3 are disclosed inU.S. Pat. Nos. 2,825,721, 3,023,203, 3,622,251, and 4,011,382 andinclude chromic acetyl acetonate, chromic halide, chromic nitrate,chromic acetate, chromic sulfate, ammonium chromate, ammoniumdichromate, or other soluble, chromium containing salts. In someembodiments, chromic acetate may be used.

The silyl chromate compounds used to prepare the silyl chromatecatalysts disclosed herein may include bis-triethylsilyl chromate,bis-tributylsilyl chromate, bis-triisopentylsilyl chromate,bis-tri-2-ethylhexylsilyl chromate, bis-tridecylsilyl chromate,bis-tri(tetradecyl)silyl chromate, bis-tribenzylsilyl chromate,bis-triphenylethylsilyl chromate, bis-triphenylsilyl chromate,bis-tritolylsilyl chromate, bis-trixylylsilyl chromate,bis-trinaphthylsilyl chromate, bis-triethylphenylsilyl chromate,bis-trimethylnaphthylsilyl chromate, polydiphenylsilyl chromate, andpolydiethylsilyl chromate. Examples of such catalysts are disclosed, forexample, in U.S. Pat. Nos. 3,324,101, 3,704,287, and 4,100,105, amongothers. In some embodiments, bis-triphenylsilyl chromate,bis-tritolylsilyl chromate, bis-trixylylsilyl chromate, andbis-trinaphthylsilyl chromate may be used. In other embodiments,bis-triphenylsilyl chromate may be used.

In some embodiments of the present disclosure, the silyl chromatecompounds may be deposited onto conventional catalyst supports or bases,for example, inorganic oxide materials. In some embodiments of thepresent disclosure, the chromium compound used to produce a chromiumoxide catalyst may be deposited onto conventional catalyst supports. Theterm “support,” as used herein, refers to any support material, a poroussupport material in one exemplary embodiment, including inorganic ororganic support materials. In some embodiments, desirable carriers maybe inorganic oxides that include Group 2, 3, 4, 5, 13 and 14 oxides, andmore particularly, inorganic oxides of Group 13 and 14 atoms. The Groupelement notation in this specification is as defined in the PeriodicTable of Elements according to the IUPAC 1988 notation (IUPACNomenclature of Inorganic Chemistry 1960, Blackwell Publ., London).Therein, Groups 4, 5, 8, 9 and 15 correspond respectively to Groups IVB,VB, IIIA, IVA and VA of the Deming notation (Chemical Rubber Company'sHandbook of Chemistry & Physics, 48th edition) and to Groups IVA, VA,IIIB, IVB and VB of the IUPAC 1970 notation (Kirk-Othmer Encyclopedia ofChemical Technology, 2nd edition, Vol. 8, p. 94). Non-limiting examplesof support materials include inorganic oxides such as silica, alumina,titania, zirconia, thoria, as well as mixtures of such oxides such as,for example, silica-chromium, silica-alumina, silica-titania, and thelike.

The inorganic oxide materials which may be used as a support in thecatalyst compositions of the present disclosure are porous materialshaving variable surface area and particle size. In some embodiments, thesupport may have a surface area in the range of 50 to 1000 square metersper gram, and an average particle size of 20 to 300 micrometers. In someembodiments, the support may have a pore volume of about 0.5 to about6.0 cm3/g and a surface area of about 200 to about 600 m2/g. In otherembodiments, the support may have a pore volume of about 1.1 to about1.8 cm3/g and a surface area of about 245 to about 375 m2/g. In someother embodiments, the support may have a pore volume of about 2.4 toabout 3.7 cm3/g and a surface area of about 410 to about 620 m2/g. Inyet other embodiments, the support may have a pore volume of about 0.9to about 1.4 cm3/g and a surface area of about 390 to about 590 m2/g.Each of the above properties may be measured using conventionaltechniques as known in the art.

In some embodiments, the support materials comprise silica, particularlyamorphous silica, and most particularly high surface area amorphoussilica. Such support materials are commercially available from a numberof sources. Such sources include the W.R. Grace and Company whichmarkets silica support materials under the trade names of Sylopol 952 orSylopol 955, and PQ Corporation, which markets silica support materialsunder various trade designations, including ES70. The silica is in theform of spherical particles, which are obtained by a spray-dryingprocess. Alternatively, PQ Corporation markets silica support materialsunder trade names such as MS3050 which are not spray-dried. As procured,all of these silicas are not calcined (i.e., not dehydrated). However,silica that is calcined prior to purchase may be used in catalysts ofthe present disclosure.

In other embodiments, supported chromium compounds, such as chromiumacetate, which are commercially available, may also be used. Commercialsources include the W.R. Grace and Company which markets chromium onsilica support materials under trade names such as Sylopol 957, Sylopol957HS, or Sylopol 957BG, and PQ Corporation, which markets chromium onsilica support materials under various trade names, such as ES370. Thechromium on silica support is in the form of spherical particles, whichare obtained by a spray-drying process. Alternatively, PQ Corporationmarkets chromium on silica support materials under trade names such asC35100MS and C35300MS which are not spray-dried. As procured, all ofthese silicas are not activated. However, if available, chromiumsupported on silica that is activated prior to purchase may be used incatalysts of the present disclosure.

Activation of the supported chromium oxide catalyst can be accomplishedat nearly any temperature from about 300° C. up to the temperature atwhich substantial sintering of the support takes place. For example,activated catalysts may be prepared in a fluidized-bed, as follows. Thepassage of a stream of dry air or oxygen through the supportedchromium-based catalyst during the activation aids in the displacementof any water from the support and converts, at least partially, chromiumspecies to Cr+6.

Temperatures used to activate the chromium-based catalysts are oftenhigh enough to allow rearrangement of the chromium compound on thesupport material. Peak activation temperatures of from about 300° C. toabout 900° C. for periods of from greater than 1 hour to as high as 48hours are acceptable. In some embodiments, the supported chromium oxidecatalysts are activated at temperatures from about 400° C. to about 850°C., from about 500° C. to about 700° C., and from about 550° C. to about650° C. Exemplary activation temperatures are about 600° C., about 700°C., and about 800° C. Selection of an activation temperature may takeinto account the temperature constraints of the activation equipment. Insome embodiments, the supported chromium oxide catalysts are activatedat a chosen peak activation temperature for a period of from about 1 toabout 36 hours, from about 3 to about 24 hours, and from about 4 toabout 6 hours. Exemplary peak activation times are about 4 hours andabout 6 hours. Activation is typically carried out in an oxidativeenvironment; for example, well dried air or oxygen is used and thetemperature is maintained below the temperature at which substantialsintering of the support occurs. After the chromium compounds areactivated, a powdery, free-flowing particulate chromium oxide catalystis produced.

The cooled, activated chromium oxide catalyst may then be slurried andcontacted with a reducing agent, fed at a selected feed rate over aselected time period, to result in a catalyst composition having a flowindex response within a selected range. The solvent may then besubstantially removed from the slurry to result in a dried, free-flowingcatalyst powder, which may be fed to a polymerization system as is orslurried in a suitable liquid prior to feeding.

In a class of embodiments, because organometallic components used in thepreparation of the catalysts and catalyst compositions of the presentdisclosure may react with water, the support material should preferablybe substantially dry. In embodiments of the present disclosure, forexample, where the chromium-based catalysts are silyl chromates, theuntreated supports may be dehydrated or calcined prior to contactingwith the chromium-based catalysts.

The support may be calcined at elevated temperatures to remove water, orto effectuate a chemical change on the surface of the support.Calcination of support material can be performed using any procedureknown to those of ordinary skill in the art, and the present inventionis not limited by the calcination method. One such method of calcinationis disclosed by T. E. Nowlin et al., “Ziegler-Natta Catalysts on Silicafor Ethylene Polymerization,” J. Polym. Sci., Part A: Polymer Chemistry,vol. 29, 1167-1173 (1991).

For example, calcined silica may be prepared in a fluidized-bed, asfollows. A silica support material (e.g. Sylopol 955), is heated insteps or steadily from ambient temperature to the desired calciningtemperature (e.g., 600° C.) while passing dry nitrogen or dry airthrough or over the support material. The silica is maintained at aboutthis temperature for about 1 to about 4 hours, after which it is allowedto cool to ambient temperature. The calcination temperature primarilyaffects the number of OH groups on the support surface; i.e., the numberof OH groups on the support surface (silanol groups in the case ofsilica) is approximately inversely proportional to the temperature ofdrying or dehydration: the higher the temperature, the lower thehydroxyl group content.

In some embodiments of the present disclosure, support materials arecalcined at a peak temperature from about 350° C. to about 850° C. insome embodiments, from about 400° C. to about 700° C. in otherembodiments, and from about 500° C. to about 650° C. in yet otherembodiments. Exemplary calcination temperatures are about 400° C., about600° C., and about 800° C. In some embodiments, total calcination timesare from about 2 hours to about 24 hours, from about 4 hours to about 16hours, from about 8 hours to about 12 hours. Exemplary times at peakcalcination temperatures are about 1 hour, about 2 hours, and about 4hours.

In some embodiments, the silyl chromate compound may be contacted withthe calcined support to form a “bound catalyst.” The silyl chromatecompound may then be contacted with the calcined support material in anyof the ways known to one of ordinary skill in the art. The silylchromate compound may be contacted with the support by any suitablemeans, such as in a solution, slurry, or solid form, or some combinationthereof, and may be heated to any desirable temperature, for a specifiedtime sufficient to effectuate a desirable chemical/physicaltransformation.

This contacting and transformation are usually conducted in a non-polarsolvent. Suitable non-polar solvents may be materials which are liquidat contacting and transformation temperatures and in which some of thecomponents used during the catalyst preparation, i.e., silyl chromatecompounds and reducing agents are at least partially soluble. In someembodiments, the non-polar solvents are alkanes, particularly thosecontaining about 5 to about 10 carbon atoms, such as pentane,isopentane, hexane, isohexane, n-heptane, isoheptane, octane, nonane,and decane. In other embodiments, cycloalkanes, particularly thosecontaining about 5 to about 10 carbon atoms, such as cyclohexane andmethylcyclohexane, may also be used. In yet other embodiments, thenon-polar solvent may be a solvent mixture. Exemplary non-polar solventsare isopentane, isohexane, and hexane. In some embodiments isopentanemay be used due to its low boiling point which makes its removalconvenient and fast. The non-polar solvent may be purified prior to use,such as by degassing under vacuum and/or heat or by percolation throughsilica gel and/or molecular sieves, to remove traces of water, molecularoxygen, polar compounds, and other materials capable of adverselyaffecting catalyst activity.

The mixture may be mixed for a time sufficient to support or react thesilyl chromate compound on the silica support. The reducing agent maythen be contacted with this slurry, where the reducing agent is fed at aselected feed rate over a selected time period to result in a catalysthaving a flow index response within a selected range. Alternatively,after supporting the silyl chromate compound on the support, and beforeadding the reducing agent, the solvent may then be substantially removedby evaporation, to yield a free-flowing supported silyl chromate onsupport. The thus supported silyl chromate may be re-slurried in thesame or a different non-polar solvent and contacted with a reducingagent to result in a selected flow index response.

Once the catalyst is supported, and in the case of chromium oxidecatalysts, activated, the chromium-based catalyst composition may thenbe slurried in a non-polar solvent, prior to the addition of thereducing agent. The supported catalyst may be chromium oxide supportedcatalysts, silyl chromate catalysts, or a mixture of both. This slurryis prepared by admixture of the supported catalyst with the non-polarsolvent. In some embodiments, the supported silyl chromate compound isnot dried before the addition of the reducing agent, but instead is leftslurried in the non-polar solvent for reasons such as reduced costs.

The chromium-based catalysts of the present disclosure are thencontacted with a reducing agent. Reducing agents used may beorganoaluminum compounds such as aluminum alkyls and alkyl aluminumalkoxides. Alkyl aluminum alkoxides, of the general formula R2AlOR, maybe suitable for use in embodiments of this disclosure. The R or alkylgroups of the above general formula may be the same or different, mayhave from about 1 to about 12 carbon atoms in some embodiments, about 1to about 10 carbon atoms in other embodiments, about 2 to about 8 carbonatoms in yet other embodiments, and about 2 to about 4 carbon atoms infurther embodiments. Examples of the alkyl aluminum alkoxides include,but are not limited to, diethyl aluminum methoxide, diethyl aluminumethoxide, diethyl aluminum propoxide, diethyl aluminum iso-propoxide,diethyl aluminum tert-butoxide, dimethyl aluminum ethoxide, di-isopropylaluminum ethoxide, di-isobutyl aluminum ethoxide, methyl ethyl aluminumethoxide and mixtures thereof. Although the examples use diethylaluminum ethoxide (DEAlE), it should be understood that the disclosureis not so limited. In the examples that follow, where DEAlE is used,other aluminum alkyls (e.g., trialkylaluminum, triethylaluminum or TEAL,etc.) or alkyl aluminum alkoxides, or mixtures thereof may be used.

The reducing agent may be added to a mixture of a supported silylchromate catalyst with a non-polar solvent in a catalyst mix vessel orother catalyst preparation vessel. The reducing agent may be added to amixture of an activated chromium oxide catalyst with a non-polar solventin a catalyst mix vessel. The reducing agent may be added to a mixtureof silyl chromate catalysts and activated chromium oxide-based catalystin a non-polar solvent in a catalyst mix vessel. When both chromiumoxide-based catalysts and silyl chromate-based catalysts are employedtogether in this disclosure, each catalyst is typically deposited on aseparate support and receives different calcination or activationtreatments prior to mixing together. Again, the reducing agent mayinclude an organoaluminum compound, an aluminum alkyl, an alkyl aluminumalkoxide such as diethylaluminum ethoxide (DEAlE), an trialkylaluminumsuch as triethylaluminum (TEAL), a mixture of DEAlE and TEAL, and otherorganoaluminum compounds, and so forth.

The addition of the reducing agent to the catalyst slurry may beconducted at elevated temperatures and under an inert atmosphere, suchas up to 7 bar (100 psig) nitrogen head pressure. For example, theslurry may be maintained at a temperature between about 30° C. and 80°C. during admixture of the reducing agent. In other embodiments, theslurry may be maintained at a temperature between about 40° C. and about60° C. In other embodiments, the slurry may be maintained at atemperature between about 40° C. and about 50° C., such as about 45° C.

To achieve a catalyst composition or reduced catalyst having a desiredflow index response, or a flow index response within a selected range,and which makes polymer with desired attributes, the reducing agent mayneed to be well-dispersed over the catalyst mixture and throughout eachparticle. Alternatively, to obtain a catalyst composition which has adifferent flow index response or polymer with other attributes, thereducing agent may need to be non-uniformly dispersed over the catalystparticles and/or within each particle. The degree of non-uniformity maybe determined by the desired polymer attributes (such as molecularweight and breadth of molecular weight distribution) and by the desiredcatalyst flow index response under a given set of reactor conditions. Tothis end, the reducing agent is added at a selected feed rate over aselected time period to the slurry of the chromium-based catalyst, wherethe slurry may be stirred at a selected agitation rate. For example, toachieve a catalyst composition with low flow index response, the totalamount of reducing agent to be combined with the catalyst slurry may beadded over a short time period and/or at a slow agitation rate.Conversely, to achieve a catalyst composition with a higher flow indexresponse, the total amount of reducing agent may be added over a longertime period. In this case the agitation rate may be slow, medium, orrapid so as to further tailor the flow index response. In some examples,the reducing agent may be added over time period ranges of 5 seconds to120 minutes, 1 to 5 minutes, 5 to 15 minutes, 10 to 110 minutes, 30 to100 minutes, and so forth. For example, where the catalyst compositionincludes a silyl chromate, the reducing agent may be added over a timeperiod ranging from about 30 seconds to about 10 minutes. After theaddition of the reducing agent, the reducing agent may be allowed toreact with the catalyst slurry for a specified reaction time. In someembodiments, the reducing agent may be allowed to react with thecatalyst slurry for a reaction time in the ranges of from about 5minutes to about 240 minutes, or about 30 minutes to about 180 minutes,and so on.

As mentioned, the flow index response may be influenced by agitation.Catalyst preparations with similar ratios or loadings of reducing agentto chromium or catalyst and made with equivalent addition rates andtimes, may result in catalysts having different flow index responses,resulting from differing degrees of agitation in the catalyst mix vesselduring the addition and reaction of the reducing agent. Agitators usefulfor performing the agitation during catalyst preparation methodsdisclosed herein may include helical ribbon agitators and conicalagitators. In some embodiments, agitators may include a combination-typeagitator, such as combination of a helical ribbon type agitator or aconical agitator with an auger, turbine impeller, paddle, or other typeof blending device, where the different agitator types may be operatedat the same or different rpm's.

Increased agitation rates may provide catalysts with a higher flow indexresponse compared with decreased agitation rates that provide catalystswith lower flow index response. One particular benefit for someembodiments is that higher agitation rates may be used to facilitate thereducing-agent addition rate to be increased (and the addition time tobe decreased) while resulting in a catalyst having an equivalent flowindex response. As used herein, “agitation rate” generally refers to thespecific rpm of the impeller for a ribbon blender or other agitationdevices where agitator diameter does not play an important role in thedegree of agitation achieved, and refers to the impeller tip speed foragitators where agitator diameter affects the degree of mixing, such asfor a turbine impeller. Agitation rates useful herein may be dependenton the size of the reactor and upon the type of impeller. In someembodiments, such as when using a helical ribbon impeller, the agitationrate may be in the range of from about 5 to about 200 rpm, from about 10to about 180 rpm, from about 15 rpm to about 50 rpm, and the like.

Other techniques such as employing fluid jet streams introduced into themix vessel, and other mixing techniques, may be utilized in addition toor in lieu of the impeller agitator to agitate or mix the slurry in themix vessel. In embodiments employing a rotating agitator having a shaftand impeller(s), a smaller batch size in certain embodiments may lead tohigher flow index response of DEAlE-reduced chromium oxide catalysts.While not wanting to be confined by theory, this may be due to one ormore of the following: better mixing at the slurry surface of anyaggregates or gels that form and/or of the DEAlE being added due to theslurry surface being below the top of the impeller; shorter overallbatch height so better top to bottom mixing of DEAlE with the solids;greater velocity of penetration of the added DEAlE stream into theslurry surface due to falling a greater height; or differences in dryingprofiles that may result from smaller batch size.

During the reduction reaction, for a relatively larger batch size, thelevel of the slurry mixture in the mix vessel may be maintained abovethe impeller region along the shaft of the agitator. For a relativelysmaller batch size, the level of the slurry mixture in the mix vesselmay be maintained in or at the impeller region along the shaft of theagitator. As can be appreciated, agitators including the aforementionedhelical ribbon agitators and other agitators generally have animpeller(s) disposed along the shaft of the agitator. In examples, theupper portion of the agitator shaft may be free of an impeller. Thus,for a larger batch size, the level of the slurry in the mix vessel mayrise to this impeller-free region at the upper portion of the agitatorshaft. On the other hand, for a small batch size in certain examples,the level of the slurry in the mix vessel may be below thisimpeller-free region, and instead in an impeller region of the agitator.

Nevertheless, reducing agent is typically added to the surface of theslurry in the mix vessel. Other locations for adding the reducing agentmay be used to further tailor the flow index response of the catalyst.Selected feed rates and selected addition times may be interruptedbriefly to allow for refill of a reducing agent feed vessel or when anempty reducing-agent supply container is replaced. It is not believedthat a brief interruption in reducing agent flow significantly affectsthe resulting flow index response of the catalyst. Moreover, the feedsystem may have a reducing-agent charge vessel large enough to avoidinterruption while a reducing-agent supply container or shipping vesselis replaced. As discussed in detail below, the reducing agent may beadded to the mix vessel such that the dispersion of the reducing agentinto the reduction reaction slurry mixture is increased.

In some embodiments, contacting of the reducing agent and thechromium-based catalyst may occur at a selected reducing agent feed rateover a selected time at a selected agitation rate, followed by aspecified subsequent catalyst drying line-out temperature, resulting ina catalyst composition having a flow index response within a selectedrange. For example, in commercial scale catalyst manufacturingequipment, increased agitation may provide a catalyst with higher flowindex response yet allow the reducing agent to be added at faster rates,reducing batch cycle time and manpower needs. In another example, whereexisting commercial scale catalyst manufacturing equipment is limited inagitation rate, the reducing agent may be added slowly to obtain adesired tailoring to a high flow index response. Moreover, the dryingtemperature or drying line-out temperature of the catalyst may bedecreased (e.g., by 10° C., 15° C., or 20° C., such as decreasing thedrying temperature to 60° C. from 70° C., 75° C. or 80° C. in certainexamples) to obtain a desired tailoring to a high flow index response.

In some exemplary embodiments, the chromium-based catalyst may be asilica-supported chromium oxide catalyst. This silica-supported chromiumoxide may be prepared from chromic acetate on silica precursors,commercially available under trade names such as Sylopol 957HS, fromW.R. Grace and Company, and C35100MS, or C35300MS, from PQ Corporation.The chromic acetate on silica precursors may be heated to temperaturesof about 600° C. for about six hours under oxidizing conditions toproduce a chromium oxide catalyst. The temperature ramp rates duringheating may be specified, for example, in the range of 40 to 120° C. perhour, and several holds at specified temperatures may be conducted forpurposes such as allowing moisture and other surface species to bereleased and purged from the vessel to enhance higher conversion of Cr+3to Cr+6. In examples, the fluidization gas is often nitrogen initially,until the end of a hold at a temperature from 300 to 500° C. in whichsome of the organic fragments are decomposed. Then a switch to air asfluidizing gas may occur in which remaining organics are combusted and atemperature exotherm occurs. In embodiments, after the oxidation step,the activated chromium oxide catalyst is cooled and transferred to anagitated catalyst mix vessel. An amount of non-polar hydrocarbonsolvent, such as isopentane, may be added to form a slurry in which thesolids are sufficiently suspended.

A selected amount of DEAlE may then be added to the chromium oxidecatalyst over an addition time period in the range of about 30 secondsto about 500 minutes, while agitating the resultant mixture at anagitation rate in the range of about 15 rpm to about 200 rpm. In otherembodiments, the selected time period may be within the range from about30 minutes to about 240 minutes; from about 60 minutes to about 180minutes in other embodiments; and from about 90 to about 120 minutes inyet other embodiments. In some embodiments, a selected amount of DEAlEmay be added to the chromium oxide catalyst over a time period in therange of about 40 to about 80 minutes, while agitating the resultantmixture at an agitation rate of 30-40 rpm. The mixture may then beallowed to react for a reaction time in the range of from about 30minutes to about 180 minutes.

In other embodiments, the chromium-based catalyst may be asilica-supported silyl chromate catalyst. This silica-supported silylchromate catalyst may be prepared from a silica support calcined attemperatures of about 600° C. for a time period in the range of fromabout one hour to about four hours and subsequently allowed to reactwith bis(triphenylsilyl)chromate, for example, in a slurry in non-polarhydrocarbon solvent such as isopentane. A selected amount of DEAlE maythen be added to the slurry of silyl chromate catalyst over an additiontime period in the range of about 0.5 to about 10 minutes, whileagitating the resultant mixture at an agitation rate in the range ofabout 15 rpm to about 50 rpm. In a particular embodiment, a selectedamount of DEAlE may be added to the silyl chromate catalyst over a timeperiod in the range of about 1 to about 3 minutes, while agitating theresultant mixture at an agitation rate in the range of 30-40 rpm. Themixture may then be allowed to react for a reaction time in the range offrom about 30 minutes to about 180 minutes.

In various embodiments, the selected agitation rate may be less than 70rpm and the selected reducing agent addition time may be less than 20minutes. In other embodiments, the selected agitation rate may begreater than 70 rpm and the selected reducing agent addition time may beless than 20 minutes. In yet other embodiments, the selected agitationrate may be greater than 70 rpm and the selected reducing agent additiontime may be greater than 20 minutes.

After addition of the reducing agent followed by a suitable period oftime to allow for reaction, such as 0 to 2 hours, the catalyst slurry isheated further to remove the non-polar solvent. The drying may result inthe slurry transitioning from a viscous slurry to a partially driedslurry or mud to a free-flowing powder. Accordingly, helical ribbonagitators may be used in vertical cylindrical mix vessels to accommodatethe varying mixture viscosities and agitation requirements. Theagitators may have single or double helical ribbons and may optionallyinclude a central shaft auger or other more complex secondary agitator.Drying may be conducted at pressures above, below, or at normalatmospheric pressure as long as contaminants such as oxygen aregenerally strictly excluded. Exemplary drying temperatures may rangefrom 0° C. to as much as 100° C., from about 40° C. to about 85° C.,from about 50° C. to about 75° C., from about 55° C. to about 65° C.,and the like. Exemplary drying times may range from about 1 to about 48hours, from about 3 to about 26 hours, from about 5 to about 20 hours,and so forth. In a particular example of a drying temperature of about60° C., the drying time is extended to about 21 hours or more in thatparticular example. Following the drying process, the catalyst may bestored under an inert atmosphere until use.

As described above, the flow index response of chromium-based catalystsmay be tailored to meet various commercial needs by the controlledaddition of a reducing agent to a slurry of supported chromium solid ina non-polar solvent under controlled agitation. For a givenchromium-based catalyst, the supported chromium solid may be slurried,contacted with a selected quantity of a reducing agent fed at a selectedfeed rate over a selected time period at a selected agitation rate,resulting in a desired chromium to reducing agent ratio or in a desiredchromium loading on the catalyst. The solvent used to slurry thecatalyst may then be removed, such as by drying at an adjustable dryingtemperature, to give a dry, free-flowing catalyst composition. Thechromium-based catalyst has a selected flow index response for makingpolymer with desired polymer attributes. This catalyst composition maythen be fed to a polymerization reactor as is or slurried in a suitableliquid prior to feeding to a polymerization reactor.

Although the general procedure outlined above may apply to chromiumcatalysts in general, the procedure may be altered according to theparticular type of chromium-based catalyst being used. For example, theabove procedure may be manipulated for silyl chromate-based catalystsand for chromium oxide-based catalysts, the latter typically requiringan activating step or an oxidizing step to generate the desired Cr+6species prior to reduction. Additionally, the process may be adjusteddepending upon whether the entire catalyst preparation is conducted, orwhether a supported chromium compound is purchased and treated accordingto embodiments described herein.

Chromium-based catalysts formed by the above described processes mayhave a chromium loading on the support ranging from about 0.15 to about3 weight percent in some embodiments; from about 0.2 to about 0.3 weightpercent in other embodiments; from about 0.4 to about 0.6 weight percentin other embodiments; and from 0.7 to about 1.2 weight percent in otherembodiments. Chromium-based catalysts formed by the above describedprocesses may have a reducing agent to chromium molar ratio ranging fromabout 0.5 to about 8 in some embodiments; from about 2 to about 7 inother embodiments; and from about 3.0 to about 5.5 in yet otherembodiments.

Exemplary Reduction of Chromium-Based Catalyst

In view of the foregoing including the aforementioned materials,equipment, and techniques, FIG. 1 is an exemplary catalyst reducingsystem 100 having a mix vessel 102 for treating a chromium-basedcatalyst 104 to give a reduced chromium-based catalyst 106 which may beused in the polymerization of olefin into polyolefin. The incomingcatalyst 104 may generally be a supported catalyst, e.g., supported onsilica such as silica dioxide or SiO2. Of course, other catalystsupports are applicable. Furthermore, the catalyst 104 may already beactivated. In certain embodiments, the chromium-based catalyst 104 isactivated in an upstream catalyst activation system (not shown) prior tobeing fed to the mix vessel 102.

The catalyst 104 stream fed to the mix vessel 102 may be a dry catalyst104 or a mixture of the catalyst 104 and an inert solvent or mineraloil, and so forth. The inert solvent may be an alkane such asisopentane, hexane, and the like. The catalyst 104 may be provided froman upstream storage vessel, feed tank, or container, for instance. Inparticular, the catalyst 104 may be pumped (via a pump) orpressured-transferred (via nitrogen or solvent pressure, for example)through piping from the storage vessel, feed tank, or container to themix vessel 102.

In one example, the catalyst 104 is a dry catalyst powder and isnitrogen-conveyed from a storage vessel. The storage vessel may be onweigh cells to indicate the amount or weight of catalyst fed to the mixvessel 102. The amount (e.g., pounds) of catalyst 104 conveyed to themix vessel 102 may be specified for the charge. A solvent 107 (e.g.,non-polar hydrocarbon solvent), such as isopentane, is added to form aslurry in the mix vessel 102 in which at least a majority of thecatalyst 104 solids are suspended. A specified amount of solvent 107 maybe added for a given batch reduction in the mix vessel 102. The solvent107 may be introduced directly to the mix vessel 102, as shown, or maybe added, for example, through the same feed port or nozzle used by thereducing agent 108, typically before the reducing agent is fed.

While the reducing system 100 may be a continuous, semi-batch, or batchsystem, the illustrated embodiment is generally a batch system in asense that a charge of catalyst 104 is fed to the mix vessel 102, acharge of solvent 107 is fed to the mix vessel 102, agitation begun, anda charge of reducing agent 108 is fed over time to the mix vessel 102for a given charge of catalyst 104. Of course, other configurations andactions are applicable. The residence time of the charge of catalyst 104in the mix vessel 102 gives reaction of substantially all of the presentreducing agent 108 with the catalyst 104 to produce the reduced catalyst106.

The reducing agent 108 supplied to the mix vessel 102 may generally bean organoaluminum compound and may be neat or diluted in a non-polarsolvent. As discussed above, a variety of reducing agents and inertsolvents may be employed. Moreover, additional solvent may be added tothe mixture in the mix vessel 102. In a particular example, the reducingagent 108 is DEAlE, and the reducing agent 108 stream is 25 weightpercent DEAlE in isopentane. Of course, the DEAlE may be diluted atother concentrations and in other solvents.

In operation, a charge of the activated catalyst 104 is fed to the mixvessel 102. A charge of solvent 107 may be fed to the mix vessel 102 andagitation started, including prior to the introduction of reducing agent108. In embodiments, the catalyst 104 may be fed in solvent to the mixvessel 102. In a particular example, the activated catalyst 104 is fedin an isopentane charge to the mix vessel 102. A reducing agent 108,also optionally diluted in solvent, is added at an adjustable feed rateto the mix vessel 102 to react with the catalyst 104. Note that forembodiments with the reducing agent 108 diluted in solvent, additionalsolvent 107 may be further added, including prior to the addition of thereducing agent 108 stream for a given batch. In one example, thereaction or reduction reaction in the mix vessel is conducted at atemperature at about 45° C., or at within 2° C. of about 45° C., and ata pressure of about 30 pounds per square inch gauge (psig). Othertemperatures and pressures are applicable.

In certain embodiments, the length of time of feeding the reducing agent108 to the mix vessel 102 may be as long as 40 minutes and greater. Atthe conclusion of feeding the reducing agent 108, the contents of themix vessel 102 may be given additional residence time for reaction ofthe reducing agent 108 with catalyst in the mix vessel 102. The catalystmay be subsequently dried, such as in place in the mix vessel 102, todrive off solvent 110 to give a product (reduced) catalyst 106 that issubstantially dry. The reduced chromium-based catalyst 106 may bedischarged to a collection vessel 112, such as a storage vessel orcontainer (e.g., cylinder), and the like. Generally, the collectionvessel 112 may have a substantially inert atmosphere.

Further, as indicated in the discussion throughout this disclosure, themix vessel 102 may typically have an agitator, e.g., agitator 210 inFIG. 2, to agitate and mix the contents (catalyst, reducing agent,solvent, etc.) in the mix vessel 102. Both the feed rate (e.g., in massper time or volume per time) of the reducing agent 108 to the mix vessel102, and the agitation rate (e.g., in revolutions per minute or rpm) ofthe mix vessel 102 agitator may be adjusted to give a desired orspecified flow index response of the reduced chromium-based catalyst106.

Additionally, after the reaction of the reducing agent 108 with thecatalyst 104 in the mix vessel 102, the produced reduced catalyst 106may be dried such as in place in the mix vessel 102. Indeed, after thereaction of the reducing agent 108 with the catalyst (in one example, ata reaction temperature of 45° C.), the catalyst drying temperature(e.g., 55° C., 60° C., 65° C., 70° C., 75° C., 80° C., 85° C., etc.) ordrying line-out temperature may be adjusted to give a desired orspecified flow index response of the reduced chromium-based catalyst106.

In the illustrated embodiment, a heat transfer system 114 provides aheat transfer medium to a jacket of the mix vessel 102 to heat or coolthe contents of the mix vessel 102 to give the desired temperature,including the reaction temperature and the subsequent catalyst dryingtemperature or drying line-out temperature, of the mix vessel 102contents. As discussed below with respect to FIG. 2, the heat transfersystem 114 may include heat exchangers to provide for cooling andheating of the heat transfer medium. Moreover, as would be plainlyunderstood by one of ordinary skill in the art with the benefit of thepresent disclosure, the mix vessel 102 contents including the catalystmay be at the reaction temperature or the drying temperature, or mayapproach and reach near (e.g., within 4° C.) the reaction temperature orthe drying temperature, depending on the temperature control schemeemployed.

In some embodiments, the heat transfer system 114 and the control system116 may directly control the temperature of the contents in the mixvessel 102. In other words, a temperature set point may be specified andinput for the contents of the mix vessel 102, and the operatingtemperature of the contents of the mix vessel 102 controlled to setpoint by adjusting the temperature of the heat transfer medium to thejacket of the mix vessel 102. Thus, for an exemplary reactiontemperature of 45° C., the temperature set point is specified as 45° C.and the contents of the mix vessel measured and maintained at 45° C.during the reduction reaction. Similarly, for an exemplary dryingtemperature of 60° C., the temperature set point is specified at 60° C.and the contents of the mix vessel measured and maintained at 60° C. Insuch embodiments, the temperature controller for the mix vessel 102contents that receives the entered set point for reaction temperatureand drying temperature may be a master controller. This mastercontroller may provide a secondary set point to a slave temperaturecontroller that adjusts the temperature of the heat transfer mediumsupply to the jacket of the mix vessel 102 to maintain the contents ofthe mix vessel 102 at the primary set point of reaction temperature ordrying temperature.

However, in other embodiments, a master/slave control configuration isnot employed. Instead, the temperature of the heat transfer medium(e.g., the supply to the jacket) is designated with a specified andentered set point as the jacket temperature for the reaction temperatureor drying temperature. Thus, for an exemplary reaction temperature of45° C., the mix vessel 102 jacket temperature set point is specified as45° C., the jacket temperature measured and maintained at 45° C. duringthe reduction reaction, and the temperature of the mix vessel 102contents is at about 45° C. at steady state during the reductionreaction. The steady-state temperature of the mix vessel 102 contentswith the jacket temperature set point as the reaction temperature maygenerally be the reaction temperature. In other words, due to theexothermic nature of the reduction reaction, the temperature of the mixvessel 102 contents may generally be the same or similar as or slightlyhigher than the jacket temperature during steady state of the reductionreaction. However, for an exemplary drying temperature of 60° C., themix vessel 102 jacket temperature set point is specified as 60° C., thejacket temperature measured and maintained at 60° C. during drying ofthe reduced catalyst 106, and the temperature of the mix vessel 102contents including the catalyst 106 reaches and lines out near 60° C.(e.g., about 64° C.) at steady state during drying. The steady-statetemperature of the mix vessel 102 contents for the jacket temperatureset point as the drying temperature is defined herein as the dryingline-out temperature. In all, for a mix vessel 102 jacket temperature asa primary set point, the contents of the mix vessel 102 may reach aline-out temperature near (e.g., within 4° C.) the jacket temperature.It should be noted that when controlling to the jacket temperatureset-point as the drying temperature, the drying line-out temperature(e.g., catalyst temperature of 64° C.) may exceed the drying temperature(e.g., jacket temperature of 60° C.) due to the heat contribution addedby the mechanical energy of the agitator or agitation, for instance,

In certain embodiments during the catalyst 106 drying, the pressure ofthe mix vessel 102 may be decreased, including incrementally, to as lowas about 1 psig or even to a vacuum to facilitate the drying of thecatalyst 106 in the mix vessel 102. During drying, including when thepressure is lowered, such as to 1 psig or to a vacuum, the temperatureof the reduced catalyst may decrease substantially below the jackettemperature and below the drying or drying line-out temperature of thecontents in the mix vessel 102. As drying proceeds further and nearscompletion, the mix vessel 102 contents temperature may climb near tothe jacket temperature and reach a substantially constant temperature.As mentioned, this substantially constant temperature of the solidmaterial may be referred to as the drying line-out temperature and iswhat may be manipulated to adjust the flow index response of thecatalyst. Generally, the drying line-out temperature may be within a fewdegrees of the jacket temperature for a heat transfer system thatcontrols the jacket temperature to set point. For instance, again, adrying temperature of 60° C. (jacket temperature) may give a dryingline-out temperature of about 64° C. (temperature of the contents in themix vessel) in a particular example. As for drying process behavior incertain examples, the pressure in the mix vessel 102 may be reduced atthe beginning of drying, and the jacket temperature set (e.g., raised)to the drying temperature of 60° C., for instance. However, the catalyst106 slurry temperature in the mix vessel 102 may initially decrease toas low as about 30° C. or lower, for example, due to solvent evaporativecooling. Generally, once the free liquid outside of the catalyst poresand on the surface of the catalyst is evaporated, the catalysttemperature may start climbing toward and beyond the drying temperature(jacket temperature of 60° C. in these examples) to a drying line-outtemperature (e.g., 64° C.). The time for the catalyst in the mix vessel102 to reach 60° C. and the eventual drying line-out temperature of 64°C. may be several hours. Thus, in certain instances, a reported dryingtime of 18 hours, for example, may represent 6-9 hours of the catalystat a drying line-out temperature (e.g., 64° C.) near (within 4° C.) thedrying temperature of 60° C. (jacket temperature). Of course, otherdrying and drying line-out temperature and times, and drying processbehaviors are applicable.

A control system 116 may provide for control and adjustment of theaforementioned process variables in the catalyst preparation andreduction. The process variables may include feed rate of reducing agent108 and the agitation rate (rpm) of the agitator. The process variablesmay include the reaction temperature, pressure, and hold time in the mixvessel 102, and the drying temperature, pressure, and time in the mixvessel 102, and so forth. The control system 116 may include any numberof units, such as a distributed control system (DCS), a programmablelogic controller (PLC), and the like.

In some embodiments, a filter/slurry system 118 may be optionallyinstalled, and employed in addition to, or in lieu of, evaporating thesolvent to dry the catalyst 106. In particular embodiments, nosignificant heat-drying of the catalyst 106 is implemented in the mixvessel 102. Instead, the catalyst 106 slurry in a solvent is dischargedfrom the mix vessel 102 to the optional filter/slurry system 118. Incertain embodiments, the temperature of the mix vessel 102 may belowered, such as to 25° C. in one example, prior to discharge of thecatalyst 106 slurry to filter/slurry system 118. Of course, otherfiltering temperatures my be employed, such as in the range of 30° C. to70° C., or higher.

In the filter/slurry system 118, the catalyst 106 slurry may be filteredto remove solvent to give a catalyst 106, with residual solvent, whichis sent to the collection vessel 112. As a further alternative, thecatalyst 106 after filtering may be re-slurried with another alkanesolvent or a mineral oil, for example, prior to being sent to thecollection vessel 112. Such avoiding of heat-drying the catalyst in themix vessel 102 and instead filtering the catalyst 106 may provide areduced catalyst 106 with a different flow index response. In certainfiltering embodiments, the flow index response is higher than ifheat-drying, which may be beneficial where a higher flow index responseis desired.

FIG. 2 is a more detailed view of the exemplary catalyst reducing system100 having the agitated mix vessel 102. Like numbered items are asdiscussed with respect to FIG. 1. The metallurgy or material ofconstruction of the mix vessel 102 may include carbon steel, stainlesssteel, nickel alloys, and so on. In certain embodiments, the mix vessel102 has a nominal diameter in the exemplary range of 60 to 80 inches(152 to 203 cm) and a volume in the exemplary range of 1,000 to 3,000gallons (3,785 to 11,355 liters). These ranges are only given asexamples and are not meant to limit embodiments of the presenttechniques. Further, the mix vessel 102 may be a jacketed vessel havinga jacket 200 for a heat transfer medium used to facilitate control ofboth the reaction temperature and the drying temperature for the mixvessel 102, as discussed below.

In the illustrated embodiment to perform the reduction, a charge ofchromium-based catalyst 104 enters at an upper portion or top surface ofthe mix vessel 102. A charge of non-polar hydrocarbon solvent 107, suchas isopentane, is also added and the agitator started to form a slurryin which the solids are at least partially suspended. The solvent 107may be introduced through a dedicated feed port, as shown. On the otherhand, the solvent 107 addition may share the same feed port or nozzlewith the reducing agent 108, typically in sequence. The reducing agent108 (e.g., neat DEAlE, DEAlE diluted in solvent, etc.) is added at anupper portion (e.g., top surface or top head) of the mix vessel 102. Alevel 202 of the mixture of solid and liquid contents is realized in themix vessel 102 during the reaction.

The addition or feed rate (e.g., in mass per time or volume per time) ofthe reducing agent 108 may be manipulated by a control valve 204 (e.g.,flow control valve) under the direction of the control system 116 orother control system. A set point of the feed rate may be specified inthe control system 116 based on or in response to the desired flow indexresponse value or range of the reduced catalyst 106. A flow sensor 206,such as a mass meter, flow orifice (i.e., with differential pressuretaps), and so on, may measure the flow rate of the reducing agent 108. Atransmitter associated with the flow sensor 206 may send a signal to thecontrol system 116 indicating the measured flow rate. The flow controlloop implemented via the control system 116, e.g., as a control block ina DCS control system 116, may adjust the valve opening position of thecontrol valve 204 to maintain the flow rate of reducing agent 108 at setpoint, such as the desired addition rate of reducing agent 108 to themix vessel 102. The control system 116 and instrumentation associatedwith the flow sensor 206 may totalize the mass of reducing-agent (e.g.,DEAlE) solution fed, and the control system 116 closes the control valve204 when the desired charge amount is fed. Alternatively, the desiredvolume of reducing agent 108 may be fed in advance into a reducing-agentcharge vessel from which reducing agent 108 solution is fed to mixvessel 102 through flow sensor 206 and control valve 204.

The catalyst 104 and the reducing agent 108 generally react in the mixvessel 102 during the addition of the reducing agent 108. Further, thecatalyst 104 and reducing agent 108 may be given more residence time(i.e., a hold time) to react in the mix vessel 102 after the addition ofthe reducing agent 108 is complete. In certain embodiments, the holdtime may be 0.5 hr, 1 hr, 1.5 hrs, 2 hrs, 2.5 hrs, 3 hrs, and so on. Avalve 208 at the bottom discharge of the mix vessel 102 or on the bottomdischarge piping as depicted, may retain the catalyst in the mix vessel102 during the addition of the reducing agent 108, during any additionalreaction or hold time, and also during the subsequent drying of thereduced catalyst 106 in the mix vessel 102. The valve 208 may be amanual or automatic block valve, or other type of valve.

The mix vessel 102 may include an agitator 210 to agitate the contentsof the mix vessel 102. The agitation may promote mixing and contact ofthe reducing agent 108 with the catalyst 104 to facilitate the reactionof the reducing agent 108 with the catalyst 104. In the illustratedembodiment, the agitator 210 has a shaft 212 and an impeller 214. Whilethe process symbol for the agitator 210 is depicted as a shaft with asimple blade impeller, the agitator 210 may be a helical ribbon agitatoror conical agitator, among others. In some embodiments, the agitator 210may include a combination-type agitator, such as combination of ahelical ribbon type agitator or a conical agitator with an impeller,turbine impeller, paddle, or other type of blending device.

Furthermore, the agitator 210 may include a motor 216 to drive theturning or rotation of the shaft 212 and impeller 214. The motor 216 mayinclude a variable-speed drive or variable-frequency drive (VFD), forexample, to facilitate adjustment of the agitation or agitator speed,e.g., the rpms of the shaft 212 and impeller 214. The VFD of the motor216 in manipulating the speed of the agitator may operate under thedirection of the control system 116 or other control system. A set pointof the agitation rate or speed (rpm) may be specified in the controlsystem 116 based on or in response to the desired flow index responsevalue or range of the reduced catalyst 106.

As mentioned, the reaction of the reducing agent 108 with the catalyst104 to give the reduced catalyst 106 may be performed at a specifiedpressure in the mix vessel and a specified temperature in the mix vessel102. The reaction pressure may be maintained (e.g., via an inert gas orvapor head pressure) at exemplary values of 15 psig, 30 psig, 50 psig,75 psig, 100 psig, and the like. The reaction temperature may bemaintained at exemplary values of 20° C., 25° C., 30° C., 35° C., 40°C., 45° C., 50° C., 55° C., 60° C., and so on. This reaction temperaturemay be either the temperature of the mix vessel 102 contents or thetemperature of the mix vessel 102 jacket 200. Also, the desired oradjusted drying temperature value (e.g., 60° C., 65° C., 70° C., 75° C.,80° C., etc.) may be input as the set point of a temperature controlleron the mix vessel 102 or input as the set point of the temperaturecontroller 222 on the heat transfer medium supply 218.

To maintain and control the reaction temperature and drying temperatureas the temperature of the contents in the mix vessel 102 or as thetemperature of the heat transfer medium supply 218, the catalystreducing system 100 may include a heat transfer system 114 that iscoupled with the jacket 200 of the mix vessel 102. The heat transfersystem 114 may include heat exchangers (heaters, cooler, condensers,etc.), vessels, pumps, piping, valves, and the like, to provide a heattransfer medium supply 218 at a desired or specified temperature to thejacket 200 of the mix vessel 102. The heat transfer system 114 may alsoreceive and process a heat transfer medium return 220 from the jacket200 of the mix vessel 102. Examples of a heat transfer medium includetempered water, treated water, demineralized water, cooling tower water,steam condensate, steam, glycols, and other heat transfer fluids.

A temperature controller 222 may rely on a temperature sensor to measureand indicate temperature of the heat transfer medium supply 218. Thetemperature controller 222 may be represented by a control logic blockin the control system 116 or other control system. The temperaturesensor associated with temperature controller 222 (and other temperaturesensors in the system 100) may include a thermocouple housed in athermowell, or a resistance temperature detector (RTD), and the like.The sensed temperature values may be transmitted or otherwise indicatedto hardware and logic of a control system (e.g., control system 116). Inresponse, the control system (via the controllers) may send outputsignals to manipulate or modulate operation of various process equipmentand valves to maintain the measured temperature at set point.

In the illustrated embodiment, the temperature controller 222 maintainsthe temperature of the heat transfer medium supply 218 at an entered setpoint. Indeed, the temperature controller 222 may direct adjustment ofthe operation of equipment and valves in the heat transfer system 114 togive the desired temperature set point of the heat transfer mediumsupply 218. This heat transfer medium supply 218 temperature may belabeled as the jacket 200 temperature of the mix vessel 102 or mayapproximate the jacket 200 temperature of the mix vessel 102. Moreover,in embodiments, the aforementioned reaction temperature and dryingtemperature may be the set point of the temperature controller 222(e.g., the temperature of the heat-transfer medium supply 218 or thejacket 200 temperature) during the catalyst reduction reaction andsubsequent drying of the reduced catalyst, respectively. The temperatureof the mix vessel 202 contents may be the reaction temperature and thedrying line-out temperature, respectively, and may approach (e.g.,within 4° C.) the jacket 200 temperature. For example, an operator mayinput a target jacket 200 temperature into the jacket 200 temperaturecontroller 222 which then acts to maintain a steady jacket 200temperature during drying of the catalyst allowing the drying catalystto gradually approach and line out near the jacket 200 temperature. Inthe illustrated embodiment, the temperature of the mix vessel 102contents may be indicated by the temperature indicator 224 having atemperature sensor 226 extending into the mix vessel 102. Thetemperature controller 222 and other temperature controllers in thesystem 100 may be logic control blocks in a control system 116, such asa DCS, and may be associated with appropriate field hardware such as atransmitter, sensor, and so forth. Again, the temperature controller 222output may direct equipment in the heat transfer system 114.

In alternate embodiments, the temperature indicator 224 on the mixvessel 102 may instead be configured as a temperature controller thatmaintains the mix vessel 102 contents at a temperature set point. Insuch embodiments, the temperature controller 222 of the heat transfermedium supply 218 may be the secondary or slave controller thatfacilitates control of temperature of the heat transfer medium supply218. As mentioned, the temperature controller 222 may send an outputsignal(s) to adjust the position of one or more valves (and/or pumps,etc.) in the heat transfer system 114. In operation, the output of theprimary temperature controller for the mix vessel 102 contents mayspecify the set point of the temperature controller 222 as the secondaryor slave on the heat transfer medium supply 218. The temperature setpoint of the temperature controller 222 as a secondary or slavecontroller for the heat transfer medium supply 218 may be higher orlower than the temperature set point of the primary temperaturecontroller of the mix vessel 102 contents. This may depend on whetherheating or cooling of the mix vessel 102 contents is being implementedto maintain the desired temperature of the mix vessel 102 contents atset point. In operation, a control scheme may direct the heat transfersystem 114 to maintain the temperature of the contents in the mix vessel102 at a desired set point. The temperature control may involve acascade control scheme, or in other words, a primary controller (e.g.,temperature controller 224) that maintains mix vessel 102 temperatureand directs a slave controller (e.g., temperature controller 222) thatadjusts temperature of the heat transfer medium supply 218. To implementand maintain a desired temperature of the mix vessel 102 contents, thedesired reaction temperature value (e.g., 45° C.) or drying temperaturevalue (e.g., 60° C.) may be specified as the set point of the primarytemperature controller on the mix vessel 102. Other temperaturecontrollers and temperature sensors may be disposed at other points inthe system 100 including on the mix vessel 102 and in the heat transfersystem 114.

In general, the temperature instrumentation may include a sensor orsensing element, a transmitter, and so forth. For a temperature elementor instrument, the sensing element may include a thermocouple, RTD, andthe like. A transmitter may convert a received analog signal from thesensing element to a digital signal for feed or transmission to acontrol system such as the control system 116. A control block in thecontrol system 116 may utilize such measured data. As mentioned withrespect to FIG. 1, the heat transfer system 114 may operate, at least inpart, under the direction of the control system 116.

The control system 116 and associated control schemes may be utilized tochange the temperature of the mix vessel 102 contents or the heattransfer medium supply 218 from the reaction temperature (e.g., in therange of 35° C. to 55° C.) to the drying temperature (e.g., in the rangeof 55° C. to 85° C.). In certain embodiments, the temperature of thecontents in the mix vessel 102 and the heat transfer medium supply 218generally increases when transitioning from the reaction temperature tothe drying temperature.

After the reaction of substantially all of the reducing agent 108 withthe catalyst 104 to give the reduced catalyst 106, the catalyst 106 maybe dried in the mix vessel 102, i.e., the solvent 110 evaporated anddriven from the mix vessel 102. The evaporated solvent 110 may dischargeoverhead from the mix vessel 102 and be collected in a recovery system,for example. The drying temperature or drying line-out temperature ofthe catalyst 106 in the mix vessel 102 may be adjusted in response to(or to adjust) the desired or specified flow index response of thecatalyst 106. The flow index response of the catalyst 106 may be afunction of the catalyst drying temperature or drying line-outtemperature in the mix vessel 102. See the examples of FIGS. 6 and 7depicting flow index of the subsequently polymerized polymer as afunction of the upstream catalyst drying temperature or drying line-outtemperature. In the illustrated embodiment of FIG. 2, the set point ofthe temperature controller 222 on the heat transfer supply medium 218may be specified and adjusted as the drying temperature (to give adesired flow index response).

The control system 116 may include control hardware, a processor, andmemory storing code executable by the processor to implement controlschemes. As mentioned with respect to FIGS. 1 and 2, the control system116 may direct and control the aforementioned process variables of theaddition feed rate of the reducing agent 108, the agitator 210 speed,the catalyst 106 drying temperature, and other process variables. In thecontrol system 116, computer-readable media may store control executablecode to be executed by associated processors including centralprocessing units, and the like. Such code executable by the processor(s)may include logic to facilitate the operations described herein.

Indeed, the control system 116 may include the appropriate hardware,software logic and code, to interface with the various processequipment, control valves, conduits, instrumentation, etc., tofacilitate measurement and control of process variables, to implementcontrol schemes, to perform calculations, and so on. A variety ofinstrumentation known to those of ordinary skill in the art may beprovided to measure process variables, such as pressure, temperature,flow rate, and so on, and to transmit a signal to the control system 116where the measured data may be read by an operator and/or used as aninput in various control functions or calculations by the control system116. Depending on the application and other factors, indication of theprocess variables may be read locally or remotely by an operator, and/orused for a variety of control purposes via the control system 116.

As discussed with respect to controlling to an entered set point ofjacket temperature as the drying temperature, a temperature controller“TC” may be situated on the jacket supply, for instance, and atemperature indicator “TI” on the slurry contents in the vessel 102.When controlling to jacket temperature as the drying temperature, a setpoint of the jacket temperature (e.g., of the heat-transfer mediumsupply) may be entered as the drying temperature. Thus, the temperatureof the contents in the vessel 102 may be a drying “line-out” temperaturethat is a few degrees different than jacket temperature. In theseexamples of jacket temperature as the drying temperature, thedirectly-controlled operating temperature may be an operating variableof the vessel (jacket temperature) but not the actual temperature of thevessel contents when controlling to the jacket temperature. Accordingly,when directly controlling and adjusting jacket temperature as dryingtemperature, the jacket temperature (e.g., heat transfer medium supply)may be the reaction temperature (e.g., 45° C.) and also the dryingtemperature (e.g., 60° C.). Thus, in embodiments, the reactiontemperature and the drying temperature may be the jacket temperaturewhich is an operating variable of the vessel 102, and with theunderstanding that the temperature of the contents in the vessel 102 mayline-out near but at a different temperature than the jackettemperature. An alternative is to control to temperature of the slurrycontents in the vessel 102, e.g., with master and slave temperaturecontrollers operating on the mix vessel contents and the mix vesseljacket, respectively.

In sum for certain examples, when controlling to jacket temperature, thedirect temperature operating variable of the vessel 102 may be thejacket temperature. The entered set point may be the jacket temperature.Therefore, for a reaction temperature of 45° C., for example, the jackettemperature (supply) may be maintained at 45° C. and the vessel 102contents slurry temperature approaches and lines out at about 45° C.,for instance. However, for a drying temperature of 60° C., for example,the jacket temperature (supply) is maintained at 60° C. and the vessel102 contents temperature lines out at about 64° C., for instance (e.g.,exceeding the jacket temperature due to heat of mechanical energyimparted by the agitator on the substantially dry catalyst). On theother hand, when controlling directly to vessel 102 contentstemperature, the direct temperature operating variable of the vessel maybe the vessel contents (slurry, catalyst) temperature. The entered setpoint may be the vessel contents slurry temperature. Therefore, for areaction temperature of 45° C., for example, the vessel contents slurrytemperature ramps to and is maintained at 45° C. For a dryingtemperature of 60° C., the vessel contents temperature ramps to and ismaintained at 60° C. Of course, as the drying proceeds, the contents inthe vessel 102 during the drying phase become primarily solids as thesolvent is evaporated and discharged overhead.

To facilitate discharge of the dried solid reduced catalyst 106, thebottom portion of the mix vessel 102 may be a conical shape with atleast a 45° slope of the walls of the cone, and up to a 60° slope orgreater. Moreover, to facilitate drying of the reduced catalyst 106, aninert gas 223 (e.g., nitrogen) may be introduced to the mix vessel 102,such as to the lower cone (as shown) or to the outlet piping. Thissupply purge of inert gas 223 may flow up through the bed of catalyst106 solids in the mix vessel once the free liquid outside the pores ofthe catalyst 106 support has evaporated. A manual or automatic valve 225is provided so that the purge of inert gas 223 may be closed and notintroduced during the reduction reaction prior to drying, for example. Arestriction orifice may be provided to limit the inert gas 223 flowrate.

As mentioned with respect to alternate embodiments, a filter/slurrysystem 118 may be optionally employed instead of significant heat-drying(evaporating of solvent) of the catalyst 106. A catalyst 106 slurryhaving solvent is discharged from the mix vessel 102 to thefilter/slurry system 118, such as at ambient temperature of in the rangeof 20° C. to 30° C., for example. The catalyst 106 slurry may befiltered by the filter/slurry system 118 to partially remove solvent togive a filtered catalyst 106 sent to the collection vessel 112. As afurther alternative, an alkane solvent or a mineral oil, for example,may be added to the filtered catalyst 106 prior to collection in thecollection vessel 112. Thus, the collection vessels 112 may hold underan inert atmosphere, for instance, either a filtered catalyst 106 and/ora slurried catalyst 106. Such avoiding of significant heat-drying of thecatalyst in the mix vessel 102, combined with the subsequent filtering,may provide a reduced catalyst 106 with a relatively higher flow indexresponse which may be beneficial where a higher flow index response isdesired.

Additionally, in accordance with embodiments of the present techniques,the mix vessel 102 may include an entrance arrangement 228 for theincoming reducing agent 108. The entrance arrangement 228 may facilitateentry of the reducing agent 108 into the mix vessel 102. In particular,the entrance arrangement 228 may direct the incoming reducing agent awayfrom the interior sidewall of the mix vessel 102, for example.

In examples, the reducing agent 108 may generally be fed to the mixvessel 102 at a relatively low flow rate. Conventionally, the reducingagent 108 may be introduced through a simple nozzle or fitting on thetop head of the mix vessel 102. However, with such a plain nozzle orfitting and especially when gradually adding reducing agent 108 over aspecified time period, the entering reducing agent 108 may fully orpartially flow along the underside of the top head and down the side ofthe mix vessel 102 instead of flowing directly to the level 202 surfacein the mix vessel 102. Consequently, dispersion of the reducing agent108 into the reaction mixture may be inhibited. Such lack of dispersionmay be more pronounced with aggregation of particles induced by reducingagent 108 giving a viscous slurry approaching gel-like behavior whichmay be a phenomenon problematic at the slurry surface near the outsidewall. This phenomenon may inhibit good dispersion of the reducing agent108 throughout the slurry.

Thus, embodiments may provide a new entrance arrangement 228 having aconduit or conduit extension 230 extending into the mix vessel 102 todirect flow of reducing agent 108. In the illustrated embodiment of FIG.2, the conduit extension 230 may be an insert positioned into or througha nozzle 232 on an upper portion (e.g., top head 234) of the mix vessel102, for example. In embodiments, the conduit or conduit extension 230may be a pipe or tube extending into the nozzle 232 and also into thevessel 102.

This conduit or conduit extension 230 may result in increased mixing anddispersion of the reducing agent 108 in the mix vessel 102 contents byguiding the entering reducing agent 108 more directly toward theagitated mixture, or toward a more mobile portion of the agitatedmixture. The conduit extension 230 may prevent the entering reducingagent 108 from flowing on the underside of the top head 234 and down theside of the vessel 102, for example. In certain embodiments, theextension 230 may direct the incoming reducing agent 108 towarddesirable locations of the surface of the reaction mixture in the mixvessel 102. For instance, in some embodiments, the conduit extension230, e.g., a pipe or tube insert, directs the reducing agent 108 to asurface location of the mixture level 202 that is 20-80%, or 50-70%, ofthe horizontal (perpendicular) distance 236 from the vessel 102 verticalcenterline or agitator 204 vertical centerline to the inside surface 238of the outside wall. The directed flow and thus improved dispersion ofreducing agent 108 due to the conduit extension 230 may increase flowindex response of the catalyst 106, and also increase catalyst 106productivity. In some embodiments, the conduit extension 230 as aninsert may be removed or a port used which does not have a conduitextension 230 when a low flow index response is desired.

Examples of chromium-based catalysts 104 that may be applicable to useof a conduit extension 230 or tube for entry of a reducing agent 108(e.g., DEAlE) may include at least chromium oxide on silica supports,such as high temperature-activated forms of: PQ Corporation C35300MS,C35300MSF (having milling of larger support particles), C36300MS, andES370; Grace Sylopol 957HS; KD Corporation KDC11C31 and KDC120120; andAGC Sci-Tech Company D-70-120A(LV) silica with chromium, and othercatalysts. Of course, other catalyst grades and types are relevant andapplicable. Lastly, additional improvements may be implemented to reduceparticle agglomeration in the mixture and thus increase dispersion ofthe reducing agent 108 in the mixture and, therefore, increase contactand reaction of the reducing agent 108 with the catalyst. For instance,in some embodiments, the support of the catalyst may be specified as anunmilled support. Such may reduce particle aggregation in the reactionslurry exacerbated by milled supports in certain examples.

In particular, taking one example as representative of some embodiments,the catalyst 104 is a PQ Corporation grade C35300MSF of chromium oxidesupported on silica that has been activated at high temperature inoxidizing atmosphere. In this representative example, use of the PQC35300MSF grade in which the oversize fraction has been milled to formsmaller particles exacerbates particle aggregation in the reactionslurry, such that the particle aggregation may occur well before theDEAlE addition is complete. This early aggregation with the milledC35300MSF grade may result from the presence of a substantial number ofirregular broken milled-smaller particles that can experience greatersurface to surface interactions than the predominantly smooth spheres ofthe unmilled C35300MS grade. In contrast, use of the unmilled C35300MSgrade in certain examples may delay significant occurrence of theparticle aggregation phenomena until after the DEAlE addition iscomplete, or close to being complete. Notably, a variant on unmilledC35300MS grade with a smaller fraction of large particles may bebeneficial. In all, the combination of (1) improved nozzle entrancearrangement 228 for the reducing agent 108 and (2) support grade choicemay increase dispersion and reaction of the reducing agent 108 in themixture in the vessel 102.

FIGS. 3A and 3B describe an embodiment of an example entrancearrangement 228 (FIG. 3B) having an exemplary conduit extension (FIG.3A). In particular, FIG. 3A is an exemplary conduit extension 230, e.g.,a simple conduit or conduit extension, a nozzle insert, or a tube, amongothers, for the entrance arrangement 228 on the mix vessel 102 for thereducing agent 108. FIG. 3B is an exemplary entrance arrangement 228 onthe mix vessel 102 for the reducing agent 108 having the example conduitextension 230 insert installed therein.

In embodiments, the exemplary conduit extension 230 is or has a conduit240 that extends into the mix vessel 102 through a neck 242 of a nozzle232 on the mix vessel 102. The portion of the conduit 240 of theextension 230 extending into the interior of the mix vessel 102 may havea length dimension 244 to provide that the incoming reducing agent 108does not flow along the underside 258 of the top head 234 of the mixvessel 102. In examples, the length dimension 244 is 0.5″, 1″, 2″, 3″,4″, 6″, 9″, 12″, or 18″, and so on.

In alternate embodiments, the conduit extension 230 may extend into thenozzle 232 but not into the mix vessel 102. In particular, the conduitextension 230 may extend into the neck 242 of the nozzle 232 but notextend past the inside surface underside 258 of the top head 234. Thusthe length dimension 244 may be represented by a negative number (e.g.,−0.5″ or −1″) in the sense that the conduit extension 230 is recessedinto the nozzle 232 and not reaching the inside surface underside 258.Such a recessed conduit extension 230 may provide that the incomingreducing agent 108 does not flow along the underside 258 of the top head234 of the mix vessel 102.

Furthermore, whether recessed in the nozzle 232 or extending into themix vessel 102, the conduit extension 230 may be arranged such that theconduit 240 directs the reducing agent 108 to a desired location on thesurface of the reaction mixture in the mix vessel 102. In examples, theentrance arrangement 228 directs the reducing agent 108 to an area onthe surface of the reaction mixture that is in a percent range (e.g.,20% to 80%, 30% to 60%, 50% to 70%, etc.) of the perpendicular distancefrom the vertical centerline of the mix vessel 102 or agitator 210 tothe vertical inside wall of the mix vessel 102 (see FIG. 2).

It should be noted that while the depicted conduit extension 230 has asimple vertical extension, e.g., end portion of conduit 240, into themix vessel 102, the conduit 240 may extend via various physicalconfigurations, including horizontal and/or sloped orientations,branching, multiple legs or tubes, sparger or distribution holes, and soon. In one embodiment, if a combination agitator is employed in which aturbine or other impeller operates at higher speed than the main helicalribbon and creates rapid downwards circulation of slurry near theagitator shaft, it may be advantageous to direct the reducing agent 108towards the flow path leading into this impeller. Moreover, the conduitextension 230 may include a distribution device such as a distributor,spray nozzle(s), multiple nozzles at the same or different radiallocations, a jet nozzle(s) to give a narrower and/or higher velocitystream, and the like, all or some of which may be installed on or viathe conduit 240. Such incorporation of additional features and differingphysical arrangements for the conduit extension 230 may beneficiallydirect and/or distribute the reducing agent 108 to a variety ofparticular locations in the mix vessel 102. Yet, on the other hand, anadvantage of the plain vertical conduit 240 tube as depicted may besimplicity in installation, low cost, less prone to fouling, ease ofmaintenance, and so forth. Further, in embodiments, a plain shortstraight extension may accomplish preventing significant flow of thereducing agent along the underside 258 of the top head and down theinside vertical wall 238 of the mix vessel 102.

To deliver reducing agent 108 to the mix vessel 102, a pipe or conduit246 routes the reducing agent 108 to the entrance arrangement 228. Theconduit 246 terminates and couples with the reducing-agent feed nozzle232 on the mix vessel 102 via a spool piece 248. In the illustratedembodiment, the terminal flange 250 of the supply conduit 246 mates withthe inlet flange 252 of the spool piece 248. A block valve (not shown)may be installed between these two mating flanges 250 and 252.

In certain examples, the reducing spool piece 248 may provide for anincreased flange size in the direction of flow. In one example, theincoming conduit 246 is 2″ nominal diameter and terminating with aflange 250 that is a 2″ flange. A 2″ block valve 251 is sandwichedbetween flanges 250 and 252. Continuing in this particular example, theextension conduit 240 is 1.25″ nominal diameter, the upstream flange 252of the reducing spool piece 248 is a 2″ by 1.25″ reducing flange, thedownstream flange 254 of the reducing spool piece 248 is a 1.25″×3″flange, and the nozzle 232 on the mix vessel 102 is a 3″ nozzle having a3″ flange 256 and a 3″ neck 242. In this example and other examples, thereducing agent 108 is introduced through the wall 258 of the top head234 of the mix vessel 102 via the conduit 240 through the nozzle 232. Inanother example, nozzle 232, neck 242, and flange 256 may be 2″ andflange 254 may be 1.25″ by 2″.

As mentioned, the reducing agent 108 may be directed away from the wallof the mix vessel 102 and to the surface level 202 of the reactionmixture in the mix vessel 102. Further, the reducing agent 108 may bedirected to a region of the mixture with relatively higher mixing, suchas away from the vessel wall and also away from close proximity to theagitator shaft 212. Lastly, it should be noted that various agitationrates with the agitator may be employed, such as 25 rpm, 30 rpm, 37 rpm,40 rpm, 60 rpm, 70 rpm, greater than 60 rpm, greater than 70 rpm, lessthan 75 rpm, and so forth.

FIG. 4 is an exemplary bar chart 400 of flow index 402 in decigrams perminute (dg/min) for polyethylene made in laboratory slurry-phasepolymerizations using reduced chromium-based catalyst. The catalyst wasreduced in an agitated mix vessel in a pilot plant prior to thelaboratory polymerizations. The bars 404, 406, 408 are the flow index ofpolyethylene produced in three respective polymerizations conducted atthe same polymerization conditions and with catalyst that had beenreduced at the same reduction conditions except with different entrancearrangements of DEAlE to the pilot-plant mix vessel.

The chromium-based catalysts employed in the three example pilot-plantmix vessel reductions had a milled C35300MS support (labeled asC35300MSF) and were activated at 600° C. prior to the reduction and thesubsequent laboratory slurry polymerizations. To reduce the catalystprior to the polymerizations, the catalyst was reduced with DEAlE insolvent hexane in the pilot-plant mix vessel. The catalysts were reducedwith DEAlE added over 40 minutes at 45° C. reaction temperature with 30to 37 rpm helical ribbon agitator speed in the pilot-plant mix vessel togive 1.53 to 1.58 wt % Al on the catalyst, and then dried at a 71° C.line-out temperature in the pilot-plant mix vessel. To subsequentlydetermine the flow index responses, olefin was polymerized in thelaboratory slurry polymerization with the reduced chromium-basedcatalysts, and the produced polyolefin tested for flow index. Thesubsequent three respective polymerizations were conducted to producepolyethylene at the same polymerization conditions. See the Examplesection below for additional details.

The first bar 404 is the resulting flow index of 20 dg/min forpolyethylene produced with a catalyst that had been reduced in thepilot-plant mix vessel having a DEAlE feed arrangement with no conduitextension or tube insert into the mix vessel. In that arrangement withno extension or insert, the DEAlE was introduced to the mix vesselthrough a simple entrance and flowed along the underside of the head anddown the inside wall to the reduction reaction mixture in the mixvessel. Thus, the DEAlE flowed to the reaction mixture at the wall, orat 100% of the distance from the vertical centerline of the mix vesselto the inside wall of the mix vessel. As indicated, the reaction mixtureincluded the chromium-oxide based catalyst, the reducing agent DEAlE,and the solvent hexane.

The second bar 406 is the resulting flow index of about 76 dg/min forpolyethylene produced with a catalyst previously reduced in thepilot-plant mix vessel having a DEAlE feed arrangement on thepilot-plant mix vessel having a conduit extension or tube insert thatdirected the DEAlE to a location on the surface of the reductionreaction mixture in the mix vessel. In particular, the conduit extensiondirected the DEAlE to a location 83% of the perpendicular distance fromthe vertical centerline of the mix vessel to the interior surface of thewall (i.e., inside wall) of the mix vessel.

The third bar 408 is the resulting flow index of about 104 dg/min forpolyethylene produced with a catalyst previously reduced in thepilot-plant mix vessel having a DEAlE feed arrangement with a conduitextension (tube insert) that like with the second bar 406 also directedthe DEAlE to the surface of the reduction reaction mixture. However, theDEAlE with respect to the third bar 408 was directed to a surfacelocation of the reaction mixture that was 67% of the perpendiculardistance from the vertical centerline of the mix vessel to the interiorsurface of the wall of the vessel.

FIG. 5 is a bar chart 500 of flow index 502 (dg/min) from gas-phasefluidized bed polymerizations in a pilot plant using reducedchromium-based catalysts that had been reduced with different DEAlE feedarrangements in a pilot-plant mix vessel. Thus, the basic differencebetween FIG. 4 and FIG. 5 is that FIG. 4 is flow index for polyethyleneproduced in a laboratory slurry polymerization, whereas FIG. 5 is flowindex for polyethylene produced in a pilot-plant gas phasepolymerization reactor. As indicated in the Examples section below, thethree catalysts represented in FIG. 5 were one similarly reducedcatalyst and two of the same three reduced catalysts represented in FIG.4.

The first bar 504 is the resulting flow index (dg/min) of about 4.4dg/min for a DEAlE feed arrangement with no conduit extension or tubeinsert on the pilot-plant mix vessel in the reduction prior topolymerization. The DEAlE was introduced to the mix vessel through asimple nozzle, and the DEAlE flowed along the underside of the top headof the mix vessel and down the inside wall of the mix vessel to thereduction reaction mixture.

The second bar 506 is the resulting flow index of about 5.3 dg/min for afeed arrangement of DEAlE on the pilot-plant mix vessel having a conduitextension or tube insert that directed the DEAlE to a location on thesurface of the reaction mixture. In particular, the conduit extensiondirected the DEAlE to a location 83% of the perpendicular distance fromthe vertical centerline of the mix vessel (or the vertical centerline ofthe agitator) to the interior surface of the outside wall (i.e., theinside wall) of the mix vessel. The third bar 508 is the resulting flowindex of about 8.2 dg/min for a feed arrangement of DEAlE with a conduitextension, which was a tube insert in this example, that directed theDEAlE to the surface of the reaction mixture at about 67% of theperpendicular distance from the vertical centerline of the mix vessel tothe interior surface of the outside wall of the vessel.

The chromium-based catalyst employed in these three pilot-plant examplereductions represented by FIG. 5 had a support that was milled C35300MS(labeled as C35300MSF), and the catalysts were activated at 600° C.prior to the reduction in the mix vessel and the subsequentpolymerization. To reduce the catalyst after activation and prior to thepolymerizations, the catalyst was reduced with DEAlE in solvent hexanein the pilot-plant mix vessel. The catalysts were reduced with DEAlEadded over 40 minutes at 45° C. reaction temperature with 30 to 37 rpmhelical ribbon agitator speed in the pilot-plant mix vessel to give 1.53to 1.58 wt % Al on the catalyst, and then dried at a 71° C. line-outtemperature in the pilot-plant mix vessel. As mentioned, to subsequentlydetermine the flow index responses, olefin was polymerized in apilot-plant gas phase reactor with the reduced chromium-based catalysts,and the produced polyolefin tested for flow index. The threepolymerizations to produce polyethylene with the three respectivereduced catalysts were conducted at the same polymerization conditions.See the Example section below for additional details.

The examples of FIGS. 4 and 5 demonstrate that for a reduction ofchromium-based catalyst with DEAlE in a blended or agitated reactionmixture of the catalyst, DEAlE, and solvent, the flow index response maybe a function of the location that the reducing agent enters the surfacelevel of the reaction mixture. In particular, the flow index responsemay increase as the entry point of the reducing agent to the surfacelevel of the reaction mixture is moved toward the vertical center of thevessel away from the outside wall. However, the flow index response maydecrease as the entry point approaches the agitator shaft, which may bea region of lower mixing. In certain examples, beneficial ranges for thereducing agent to meet the surface of the reaction mixture are in thedistance range of 20% to 80%, 30% to 70%, and 50% to 70%, of thedistance from the vertical centerline of the mix vessel or agitatorshaft to the inside surface or wall of the mix vessel. Moreover, fortypical alkane solvents, it should be noted that the catalyst flow indexresponse results from these example reductions of exemplarychromium-based catalysts are believed substantially independent of theparticular alkane solvent employed in the reduction. For instance, it isnot expected the flow index results would be significantly different incertain embodiments if the solvent isopentane were employed instead ofhexane. Lastly, it also should be noted that while the entrancearrangement for the reducing agent is depicted in FIG. 2 at a topportion of the mix vessel, the entrance arrangement may also be at aside of the mix vessel or on a bottom portion of the mix vessel. In oneembodiment, the entrance arrangement includes a conduit extending into anozzle on a bottom portion of the mix vessel. In operation of such anembodiment, the reducing agent enters directly into the slurry contentsin the mix vessel through conduit extending into or through the bottomnozzle.

FIG. 6 is a plot 600 of a fitted curve 602 of catalyst flow index 604(dg/min) of produced polyethylene in laboratory slurry-phasepolymerizations with catalyst that had been reduced in a pilot-plant mixvessel at a drying line-out temperature 606 (in ° C.). The catalystswere reduced in the pilot-plant mix vessel with DEAlE of differentcharges of the same type (grade) of chromium-based catalyst. Thechromium-based catalysts were made on C35300MSF support activated at600° C., then reduced in the mix vessel with DEAlE added over 40 minutesat 45° C. reaction temperature with 30 rpm helical ribbon agitator speedto give 1.53 to 1.58 wt % Al on the catalyst. The reductions of thechromium-based catalyst with DEAlE were performed in a pilot-plant mixvessel in the presence of an alkane solvent.

The DEAlE was added to the pilot-plant mix vessel using a tube insert todirect the DEAlE away from the wall of the pilot-plant mix vessel. Thedrying of the reduced catalyst in the pilot-plant mix vessel at thedrying temperature 606 occurred after substantial completion of thereaction of the DEAlE with the catalyst during a 1 hour reaction hold.To accomplish the drying, the pressure in the pilot plant mix vessel wasreduced and the temperature of the jacket increased to slightly abovethe drying line-out temperature 606 to evaporate and drive off thesolvent. In these examples, the drying time represents the length oftime from when the vessel pressure was reduced and the vessel jackettemperature increased until the jacket temperature decreased and thevessel pressure raised.

To subsequently determine the catalyst flow index 604 values, therespective batches of reduced chromium-based catalyst were used inlaboratory polymerizations of olefin into polyolefin under the same orsimilar polymerization conditions. Samples of the respective producedpolyolefin were tested to determine flow index of the polyolefin, andthus give comparable flow index values of the same catalyst type (grade)subjected to different catalyst drying line out temperatures 606.

FIG. 7 is a plot 700 of a fitted curve 702 of catalyst flow index 704(dg/min) from gas-phase fluid bed polymerizations in a pilot plantversus catalyst drying line-out temperature 706 (in ° C.) forpilot-plant mix vessel reductions with DEAlE of different charges of thesame type (grade) of chromium-based catalyst. The chromium-basedcatalysts were made on C35300MSF support activated at 600° C., thenreduced with DEAlE added over 40 minutes at 45° C. reaction temperaturewith 30 rpm helical ribbon agitator speed to give 1.53 to 1.58 wt % Alon the catalyst. These catalysts were the same three catalysts tested inthe lab polymerizations of FIG. 6.

The reductions of the chromium-based catalyst with DEAlE were carriedout in a pilot-plant mix vessel in the presence of an alkane solvent.The DEAlE was added to the pilot mix vessel using a tube insert todirect the DEAlE away from the wall of the blender. The drying of thereduced catalyst at the drying temperature 706 in the pilot mix vesseloccurred after substantial completion of the reaction of the DEAlE withthe catalyst during a 1 hour reaction hold. To accomplish the drying,the pressure in the pilot plant mix vessel was reduced and thetemperature of the jacket (i.e., the temperature of the heat transfermedium in the jacket) of the pilot-plant mix vessel increased toslightly above the drying line out temperature 706 to evaporate anddrive off the solvent. In these examples, the drying time, i.e., thelength of time from when the vessel pressure was reduced and the jackettemperature began to be increased until the jacket began to be cooledand the pressure was raised again, was 16 hours. To subsequentlydetermine the catalyst flow index 704 values, the respective batches ofreduced chromium-based catalyst were used in gas-phase fluidized bedpilot plant polymerizations of olefin into polyolefin under the same orsimilar polymerization conditions. Samples of the respective producedpolyolefin were tested to determine flow index of the polyolefin, andthus give flow index values 704 of the catalyst.

The examples in FIGS. 6 and 7 demonstrate that for a reduction ofchromium-based catalyst with DEAlE in a blended or agitated reactionmixture of the catalyst, DEAlE, and solvent, the flow index response maybe a function of the subsequent catalyst drying line out temperature toevaporate and drive off the solvent. In particular, the flow indexresponse may increase as the catalyst drying line-out temperature isreduced over certain ranges of drying temperature. In the examples, thecatalyst flow index 604, 704 increased only slightly or negligibly whenthe drying temperature 606, 706 was reduced from 80° C. to 70° C. Incontrast, the catalyst flow index 604, 704 increased significantly whenthe drying temperature 606, 706 was reduced from 80° C. to 60° C. orfrom 70° C. to 60° C.

FIG. 8 is a method 800 of preparing a chromium-based catalyst forsubsequent use in the polymerization of an olefin into a polyolefin.This method 800 of preparing a chromium-based catalyst for theproduction of polyolefin involves treating the catalyst to reduce thecatalyst. As discussed below, the method 800 includes adjusting a dryingtemperature of the catalyst.

The method 800 begins at block 802, with the contacting of achromium-based catalyst, e.g., supported and activated, with a reducingagent in a solvent to lower an oxidation state of chromium in thechromium-based catalyst to give a reduced chromium-based catalyst. Theoxidation state may be reduced from +6 (activated) to +2. The chromium+6 may instead be reduced to chromium +3. Some of the chromium +6 maynot be reduced but remain an oxidation state of +6. Thus, in certainembodiments, the produced reduced chromium-based catalyst resulting fromthe method 800 may include some chromium +6 that has not been reduced,and may include chromium reduced to oxidation states of +2 and/or +3.

The contacting and reacting of the reducing agent with thechromium-based catalyst to reduce the chromium-based catalyst may occurin a mix vessel. The reducing agent may be an organoaluminum compound(e.g., DEAlE). The solvent may be an alkane. The contacting of thechromium-based catalyst with the reducing agent may result in reactingof the chromium-based catalyst with the reducing agent to give thereduced chromium-based catalyst. Moreover, the chromium-based catalystmay be contacted with the reducing agent in the solvent at a reactiontemperature lower than the subsequent drying temperature.

The reduced chromium-based catalyst may be dried at a drying temperatureor drying line-out temperature, as indicated in block 804. In certainembodiments, the reaction temperature is in the range of 20° C. to 60°C., and the drying temperature or drying line-out temperature is in therange of 50° C. to 90° C. The drying temperature or drying line-outtemperature may be adjusted to change the flow index response of thereduced chromium-based catalyst, as indicated in block 806. Indeed, themethod 800 may involve specifying the drying temperature or dryingline-out temperature to give a desired flow index response of thereduced chromium-based catalyst. For a desired high flow index response,the drying temperature or the drying line-out temperature may bespecified at less than 65° C. or 68° C., for example. Other preferredvalues for the drying temperature or the drying line-out temperature maybe specified at less than 75° C. or 76° C., for example.

The drying of the reduced chromium-based catalyst may involveevaporating and/or filtering the solvent from the catalyst mixture. Thedrying may include reducing the pressure of the mixture of the reducedchromium-based catalyst and the solvent to facilitate evaporating and/orfiltering the solvent from the mixture. For employment of a mix vesselin the reduction of the catalyst, the evaporating of solvent viaheat-drying of the catalyst may include increasing an operatingtemperature of the mix vessel from the reaction temperature to thedrying temperature or drying line-out temperature. Furthermore, theevaporating of the solvent may include reducing an operating pressure ofthe mix vessel. In all, the evaporated solvent may discharge from themix vessel. It should be noted that where drying the catalyst includesfiltering the reduced chromium-based catalyst to remove the solvent (inlieu of significant evaporation of the solvent), the mixture of catalystand solvent may be filtered at a lower temperature (e.g., less than 30°C.) downstream of the mix vessel to increase the flow index response insome instances. Further, the filtered catalyst may then be subjected toheat drying in alternate examples. Lastly, it should be noted thatduring drying, whether by evaporation and/or filtering, a majority ofthe solvent may be removed from the catalyst, leaving residual solventwith the catalyst in certain instances.

The dried (and/or filtered) reduced chromium-based catalyst may becollected (block 808) for supply or distribution to a polymerizationreactor or polymerization reactor system. In certain embodiments, thereduced chromium-based catalyst may discharge to a storage containerfrom the mix vessel conducting the reduction and drying of the catalyst.Indeed, the method may further include feeding, at block 810, thereduced chromium-based catalyst to a polymerization reactor. At block812, an olefin is polymerized into a polyolefin in presence of thereduced chromium-based catalyst.

In sum, an embodiment includes a method of preparing a chromium-basedcatalyst such as a chromium oxide catalyst, for the polymerization of anolefin into a polyolefin. The method includes contacting achromium-based catalyst with a reducing agent (e.g., organoaluminumcompound, DEAlE, TEAL, etc.) in a solvent such as alkane to lower anoxidation state of chromium in the chromium-based catalyst to give areduced chromium-based catalyst. The chromium-based catalyst may be anactivated and supported chromium-based catalyst. The contacting of thechromium-based catalyst with the reducing agent may react thechromium-based catalyst with the reducing agent to give the reducedchromium-based catalyst. Further, in this embodiment, the methodincludes drying the reduced chromium-based catalyst at a drying line-outtemperature, and adjusting the drying line-out temperature to change theflow index response of the reduced chromium-based catalyst. Drying mayinvolve evaporating the solvent, reducing a pressure of the mixture, andso on.

In examples, the chromium-based catalyst may be contacted with thereducing agent in the solvent at a reaction temperature lower than thedrying line-out temperature, and wherein the reaction temperature is inthe range of 20° C. to 60° C., and the drying line-out temperature is inthe range of 40° C. to 90° C. In particular examples, the drying may beinitiated after substantially all of the reducing agent contacted withthe chromium-based catalyst has been consumed in a reaction of thereducing agent with the chromium-based catalyst. In some examples, thedrying may include filtering the reduced chromium-based catalyst toremove solvent at a temperature of less than 30° C., for instance. Themethod may include collecting the reduced chromium-based catalyst forsupply to a polymerization reactor. The method may include feeding thereduced chromium-based catalyst to a polymerization reactor topolymerize an olefin into a polyolefin.

An additional embodiment includes a method of preparing a chromium-basedcatalyst for the production of polyolefin, the method includingcontacting a chromium-based catalyst with a reducing agent in presenceof a solvent in a mix vessel to produce a reduced chromium-basedcatalyst. The method includes evaporating the solvent at a dryingtemperature to dry the reduced chromium-based catalyst, and specifyingthe drying temperature or drying line-out temperature to give a desiredflow index response of the reduced chromium-based catalyst. Exemplaryspecified values for drying temperature or drying line-out temperatureinclude than 65° C., less than 68° C., less than 75° C., in the range of65° C. to 75° C., less than 76° C., in the range of 75° C. to 85° C.,and so on. Evaporating may be accommodated by increasing an operatingtemperature of the mix vessel from a reaction temperature to the dryingtemperature. Evaporating the solvent may involve increasing the jackettemperature of the mix vessel from a reaction temperature to the dryingtemperature, and/or reducing an operating pressure of the mix vessel.The method may include polymerizing an olefin into a polyolefin inpresence of the reduced chromium-based catalyst in a polymerizationreactor.

Yet another embodiment includes a catalyst reducing system includes amix vessel to agitate a mixture of a chromium-based catalyst, a reducingagent, and a solvent to produce a reduced chromium-based catalyst foruse in the polymerization of an olefin into a polyolefin. In thisembodiment, the catalyst reducing system includes a heat transfer systemto provide a heat transfer medium to a jacket of the mix vessel toevaporate the solvent and dry the reduced chromium-based catalyst at adrying temperature or drying line-out temperature. A control system isconfigured to adjust the drying temperature or drying line-outtemperature in response to a measured flow index response of the reducedchromium-based catalyst. In examples, a supply temperature of the heattransfer medium to the jacket is the drying temperature, and wherein atemperature of the mixture is a drying line-out temperature. Moreover,the control system may be configured to automatically adjust the dryingtemperature or drying line-out temperature based on a predeterminedrelationship of flow index response with drying temperature or dryingline-out temperature.

Lastly, yet another embodiment is a method including preparing achromium oxide catalyst for the polymerization of an olefin into apolyolefin. The preparing includes: (1) mixing the chromium oxidecatalyst with a reducing agent (e.g., aluminum alkyl, alkyl aluminumalkoxide, etc.) in a solvent (e.g., alkane) to give a reduced chromiumoxide catalyst; (2) removing solvent from the reduced chromium oxidecatalyst at a specified temperature set point; and (3) adjusting thespecified temperature set point to give a desired flow index response ofthe reduced chromium oxide catalyst. The method includes collecting thereduced chromium oxide catalyst for delivery to a polyolefinpolymerization reactor.

FIG. 9 is a method 900 of preparing a chromium-based catalyst forpolyolefin production. The method 900 treats the chromium-based catalystfor the polymerization of an olefin into a polyolefin. As discussedbelow, the method 900 includes feeding a reducing agent to a mix vesselthrough an entrance arrangement of the mix vessel to direct the reducingagent into the mix vessel. The entrance arrangement may include aconduit extension or conduit extending into the mix vessel.

At block 902, a chromium-based catalyst is fed to a mix vessel. Thefeeding of the catalyst may involve charging the catalyst, or adding abatch or charge of the chromium-based catalyst to the mix vessel. Thechromium-based catalyst may be an activated and/or supportedchromium-based catalyst. If supported, the support may be an unmilledsupport to potentially reduce particle agglomeration in the reactionmixture in the mix vessel in certain embodiments.

At block 904, a reducing agent, such as an organoaluminum compound, isintroduced (block 904) to the mix vessel through an entrance arrangementhaving a conduit extension or conduit extending into the mix vessel. Thereducing agent may be received at the entrance arrangement of the mixvessel in a stream having the reducing agent and a solvent, for example.The stream having the reducing agent and solvent may travel through theconduit extension or conduit into the mix vessel. Additional solvent maybe added to the mix vessel prior to, during, and/or after addition ofthe reducing agent.

In certain embodiments, the conduit may have an extending length of atleast 0.5 inch, 2 inches, 4 inches, 6 inches, and so on, into the mixvessel from an upper inside surface of the mix vessel. The conduit orconduit extension may extend through an upper portion of the mix vessel,and direct the entering stream having the reducing agent toward asurface of the mixture level in the mix vessel. The conduit may extendinto the mix vessel through a top head of the mix vessel, and terminatein a designated vapor space of the mix vessel.

In some embodiments, the conduit or conduit extension is an insertthrough a nozzle of the mix vessel. In particular embodiments, theconduit extension or conduit may be a nozzle insert providing a tubethrough a nozzle of the mix vessel. In some examples, the conduitextension or conduit extends at least 2 inches into the mix vesselthrough a nozzle of the mix vessel, and wherein the stream having thereducing agent is introduced to the mix vessel through the conduitextending through the nozzle of the mix vessel. In a particular example,the conduit extension or conduit introducing the reducing agent into themix vessel may direct the entering reducing agent, or an entering streamhaving the reducing agent, toward a location of the mixture surface in arange of about 20% to 80%, or about 50% to 70%, of a perpendiculardistance from a vertical centerline of the mix vessel (or verticalcenterline of the agitator shaft) toward an inside diameter wall (insidesurface of vertical outside wall) of the mix vessel.

Other embodiments of the conduit extension are applicable. For example,the conduit extension may be a dip tube. In particular, the reducingagent may be added through a conduit extension that is a dip tubeextending past the mix-vessel vapor space to below the level of thecontents in the mix vessel. In another embodiment, the conduit extensionmay be recessed in the reducing-agent feed nozzle. In particular theconduit extension may extend into the reducing-agent feed nozzle on themix vessel but not into the mix vessel.

Lastly, with respect to the addition (block 904) of reducing agent tothe mix vessel, the reducing agent may be added to the mix vessel otherthan through the aforementioned conduit extension. For example, in analternate embodiment, the reducing agent may be added through a sidenozzle or bottom nozzle on the mix vessel below the level of thereduction reaction mixture. In general, the reducing agent may be addedto the mix vessel such that it does not travel down the inside wall ofthe mix vessel, and/or that promotes the mixing of the reducing agentwith the reduction reactor mixture.

At block 906, the mixture of the chromium-based catalyst, the reducingagent, and a solvent in the mix vessel continues to be agitated topromote contact of the reducing agent with the chromium-based catalystto give a reduced chromium-based catalyst. The agitation of the mixturemay disperse the reducing agent in the mixture to promote reaction ofthe reducing agent with the chromium-based catalyst to give a reducedchromium-based catalyst.

The reduced chromium-based catalyst is dried in the mix vessel, asindicated by block 908. The drying may include evaporating the solventin the mix vessel and discharging the evaporated solvent overhead fromthe mix vessel. The reduced chromium-based catalyst may be collected(block 910) for supply to a polymerization reactor. In one example, thereduced chromium-based catalyst may be discharged from the mix vessel toa storage container for distribution to a polymerization reactor system.The reduced chromium-based catalyst may be fed (block 912) to apolymerization reactor to polymerize (block 914) an olefin into apolyolefin in presence of the reduced chromium-based catalyst.

In sum, an embodiment provides a method of preparing a chromium-basedcatalyst for the polymerization of an olefin into a polyolefin. Themethod includes feeding the chromium-based catalyst to a mix vessel,introducing a stream having a reducing agent into the mix vessel througha conduit extending into a nozzle of the mix vessel. Further, the methodincludes agitating a mixture of the chromium-based catalyst, thereducing agent, and a solvent in the mix vessel to promote contact ofthe reducing agent with the chromium-based catalyst to give a reducedchromium-based catalyst. In certain instances, the conduit extendsthrough the nozzle into the mix vessel past an interior surface of themix vessel. In one instance, the conduit extends at least 0.5 inch intothe mix vessel through the nozzle of the mix vessel, and wherein thestream having the reducing agent is introduced to the mix vessel throughthe conduit extending through the nozzle of the mix vessel. In someinstances, the conduit may extend at least 2 inches into the mix vesselthrough the nozzle. In particular examples, the conduit may have anextending length of at least 6 inches into the mix vessel from an upperinside surface of the mix vessel. The conduit may extend through thenozzle on an upper portion of the mix vessel and direct the streamhaving the reducing agent to a surface of the mixture in the mix vessel.Indeed, the conduit may extend through the nozzle on a top head of themix vessel and terminate in a vapor space of the mix vessel. On theother hand, the conduit may be a dip tube that extends through thenozzle into the mix vessel to below a level of the mixture. The conduitmay direct the stream having the reducing agent toward a location on themixture surface, for example, in a range of 20% to 80% of aperpendicular distance from a vertical centerline of the mix vessel toan inside wall of the mix vessel. Further, reducing agent may beintroduced to the mix vessel through a second nozzle on a bottom portionof the mix vessel. The level of the mixture in the mix vessel may bemaintained in or at an impeller region of an agitator of the mix vessel.On the other hand, prior to drying the reduced chromium-based catalystin the mix vessel, the level of the mixture in the mix vessel may bemaintained above an impeller region of an agitator of the mix vessel.Lastly, the method may involve where the conduit extending into thenozzle of the mix vessel extends into the mix vessel and comprises adistributor or spray nozzle, or both. In certain configurations, theconduit extending into at least the nozzle of the mix vessel and isconfigured to direct a jet of the reducing agent to penetrate to below asurface of a level of a mixture in the mix vessel to facilitate mixingof the mixture in the mix vessel.

Another embodiment provides for a method of treating a chromium-basedcatalyst for polyolefin production, the method including adding a chargeof chromium-based catalyst to a mix vessel, and introducing a reducingagent into the mix vessel through a conduit extension that extends atleast 0.5 inch into the mix vessel and terminates in a designated vaporspace of the mix vessel. The method includes agitating a mixture of thechromium-based catalyst, reducing agent, and a solvent in the mix vesselto disperse the reducing agent in the mixture to promote reaction of thereducing agent with the chromium-based catalyst to give a reducedchromium-based catalyst. The conduit extension may be an insert througha nozzle of the mix vessel, and may direct the reducing agent toward asurface of the mixture level in the mix vessel. For example, the conduitextension may direct the reducing agent toward a location of the mixturelevel in a range of 20% to 80% of a perpendicular distance from avertical centerline of the mix vessel to an inside surface of a wall ofthe mix vessel. Moreover, the method may include maintaining a level ofthe mixture in the mix vessel at an impeller region of a shaft of anagitator of the mix vessel. The method may include discharging thereduced chromium-based catalyst from the mix vessel to a storagecontainer for distribution to a polymerization reactor system. Lastly,the method may include polymerizing an olefin into a polyolefin inpresence of the reduced chromium-based catalyst in a polymerizationreactor.

Yet another embodiment includes a reducing system for chromium-basedcatalyst may include a catalyst feed system to provide a chromium-basedcatalyst to a mix vessel, a reducing agent supply system to provide areducing agent to the mix vessel, and the mix vessel to hold a mixturehaving the chromium-based catalyst, the reducing agent, and a solvent toproduce a reduced chromium-based catalyst for use in the polymerizationof an olefin into a polyolefin. The mix vessel may include an agitatorto agitate the mixture, and an entrance arrangement for the reducingagent, the entrance arrangement having a conduit or a conduit extensionto receive and direct the reducing agent into the mix vessel. Thereducing agent may include an organoaluminum compound, an alkyl aluminumalkoxide such as diethylaluminum ethoxide (DEAlE), an aluminum alkylsuch as triethylaluminum (TEAL), a mixture of DEAlE and TEAL, and soforth. As indicated, the chromium-based catalyst may be a chromium oxidecatalyst.

In certain instances, the conduit extension extends into an interior ofthe mix vessel and directs the reducing agent to a vapor space of themix vessel. The conduit extension may direct the reducing agent awayfrom an inside surface of the mix vessel toward the mixture such astoward a top surface of the mixture level. In particular examples, theconduit extension directs the reducing agent toward a location of asurface of the mixture level that is 20% to 80%, or 50% to 70%, of theperpendicular distance from a vertical centerline of the mix vessel toan inside surface of a vertical wall of the mix vessel. The verticalcenterline of the agitator may be substantially the same as a verticalcenterline of the mix vessel. In certain embodiments, the conduitextension may be a nozzle insert through a nozzle of the mix vessel, thenozzle insert being a tube that terminates in a vapor space of the mixvessel. On the other hand, the conduit extension could be a dip tubethat extends past the vapor space below the level (surface) of contentsof the mix vessel.

In general, the reducing agent may be added to the mix vessel such thatthe reducing agent does not go predominantly go into the aggregate ringaround the outer upper surface of the slurry, and so that the dispersionof the reducing agent into the reduction reaction slurry mixture isincreased. For example, the reducing agent may be introduced through aconduit extension or conduit insert into the vapor space of the mixvessel or to below the slurry surface away from the inside wall. In thecase of the conduit or tube insert as a dip tube to below the surfacelevel, the dip tube may extend below the mixture surface between theagitator shaft and the outer helical ribbon(s), for example. The diptube may have multiple exit holes below the surface level. In anotherconfiguration, the tube insert does not extend into the vessel butinstead is recessed in a feed nozzle on the top head of the mix vessel,such that the reducing agent flows to a desired location on the surfaceof the slurry away from the inside wall of the mix vessel. Also, in yetother embodiments, the reducing agent may be added to the mix vessel viaa port or nozzle on a bottom portion of the vessel. If so, the reducingagent feed may be split between the bottom port or nozzle and a port ornozzle on the top head.

The catalyst reducing system may include a flow control valve tomodulate the flow rate of the reducing agent to the entrance arrangementof the mix vessel. The system may have a variable drive to modulate anagitation rate of the mixture by the agitator, wherein the agitationrate may be in revolutions per unit of time of a shaft of the agitator.Further, a heat transfer system may provide a heat transfer medium to ajacket of the mix vessel to maintain a temperature of the heating mediumin the jacket or to maintain a temperature of the contents in the mixvessel. A control system may facilitate adjusting agitation rate inrevolutions per time of the agitator to give a desired flow indexresponse of the reduced chromium-based catalyst. The same or differentcontrol system may facilitate adjusting flow rate of the reducing agentto the entrance arrangement of the mix vessel to give a desired flowindex response of the reduced chromium-based catalyst, and alsofacilitate adjusting a drying temperature of the reduced chromium basedcatalyst in the mix vessel to give a desired flow index response of thereduced chromium-based catalyst.

Polymerization Processes

Catalysts formed by the above described processes, as well as thecatalyst prepared inline discussed below, may be used in thepolymerization of olefins by suspension, solution, slurry, and gas phaseprocesses, using known equipment and reaction conditions, and are notlimited to any specific type of polymerization system. Generally, olefinpolymerization temperatures may range from about 0 to about 300° C. atatmospheric, sub-atmospheric, or super-atmospheric pressures. Inparticular, slurry or solution polymerization systems may employsub-atmospheric, or alternatively, super-atmospheric pressures, andtemperatures in the range of about 40 to about 300° C.

Liquid phase polymerization systems such as those described in U.S. Pat.No. 3,324,095, may be used in embodiments of this disclosure. Liquidphase polymerization systems generally comprise a reactor to whicholefin monomers and catalyst compositions are added. The reactorcontains a liquid reaction medium which may dissolve or suspend thepolyolefin product. This liquid reaction medium may comprise an inertliquid hydrocarbon which is non-reactive under the polymerizationconditions employed, the bulk liquid monomer, or a mixture thereof.Although such an inert liquid hydrocarbon may not function as a solventfor the catalyst composition or the polymer obtained by the process, itusually serves as solvent for the monomers used in the polymerization.Inert liquid hydrocarbons suitable for this purpose may includeisobutane, isopentane, hexane, cyclohexane, heptane, octane, benzene,toluene, and mixtures and isomers thereof. Reactive contact between theolefin monomer and the catalyst composition may be maintained byconstant stirring or agitation. The liquid reaction medium whichcontains the olefin polymer product and unreacted olefin monomer iswithdrawn from the reactor continuously. The olefin polymer product isseparated, and the unreacted olefin monomer and liquid reaction mediumare typically recycled and fed back into the reactor.

Some embodiments of this disclosure may be especially useful with gasphase polymerization systems, at superatmospheric pressures in the rangefrom 0.07 to 68.9 bar (1 to 1000 psig), from 3.45 to 27.6 bar (50 to 400psig) in some embodiments, from 6.89 to 24.1 bar (100 to 350 psig) inother embodiments, and temperatures in the range from 30 to 130° C., orfrom 65 to 110° C., from 75 to 120° C. in other embodiments, or from 80to 120° C. in other embodiments. In some embodiments, operatingtemperatures may be less than 112° C. Stirred or fluidized bed gas phasepolymerization systems may be of use in embodiments of this disclosure.

Generally, a conventional gas phase, fluidized bed process is conductedby passing a stream containing one or more olefin monomers continuouslythrough a fluidized bed reactor under reaction conditions and in thepresence of a catalyst composition at a velocity sufficient to maintaina bed of solid particles in a suspended state. A stream containingunreacted monomer is continuously withdrawn from the reactor,compressed, cooled, optionally partially or fully condensed, andrecycled back to the reactor. Product is withdrawn from the reactor andreplacement monomer is added to the recycle stream. Gases inert to thecatalyst composition and reactants may also be present in the gasstream. The polymerization system may include a single reactor or two ormore reactors in series.

Feed streams may include olefin monomer, non-olefinic gas such asnitrogen and hydrogen, and may further include one or more non-reactivealkanes that may be condensable in the polymerization process forremoving the heat of reaction. Illustrative non-reactive alkanesinclude, but are not limited to, propane, butane, isobutane, pentane,isopentane, hexane, isomers thereof and derivatives thereof. The feedsmay enter the reactor at a single or multiple and different locations.

Further, the polymerization process is typically conducted substantiallyin the absence of catalyst poisons such as moisture, oxygen, carbonmonoxide and acetylene. However, oxygen can be added back to the reactorat very low concentrations to alter the polymer structure and itsproduct performance characteristics. Oxygen may be added at aconcentration relative to the ethylene feed rate to the reactor of about10 to 600 ppbv, and more preferably about 10 to 500 ppbv. Organometalliccompounds may be employed as scavenging agents to remove catalystpoisons, thereby increasing the catalyst activity, or for otherpurposes. Examples of organometallic compounds that may be added includemetal alkyls, such as aluminum alkyls. Conventional adjuvants may alsobe used in the process, provided they do not interfere with themechanism of the catalyst composition in forming the desired polyolefin.In some embodiments, hydrogen gas may be added. The use of hydrogenaffects the polymer molecular weight and distribution, and ultimatelyinfluences the polymer properties. For the purpose of polymerizationwith chromium-based catalysts of the current invention, the gas moleratio of hydrogen to ethylene in the reactor may be in the range ofabout 0 to 0.5, in the range of 0.01 to 0.4 and in the range of 0.03 to0.3.

An illustrative catalyst reservoir suitable for continuously feeding drycatalyst powder into the reactor is shown and described in U.S. Pat. No.3,779,712, for example. A gas that is inert to the catalyst, such asnitrogen or argon, is preferably used to carry the catalyst into thebed. In another embodiment the catalyst is provided as a slurry inmineral oil or liquid hydrocarbon or mixture such, as for example,propane, butane, isopentane, hexane, heptane or octane. An illustrativecatalyst reservoir is shown and described in WO 2004094489. The catalystslurry may be delivered to the reactor with a carrier fluid, such as,for example, nitrogen or argon or a liquid such as for exampleisopentane or other C3 to C8 alkane.

In order to achieve the desired density ranges in the copolymers it isnecessary to copolymerize enough of the comonomers with ethylene toachieve a level of about 0 to anywhere from 5 to 10 weight percent ofthe comonomer in the copolymer. The amount of comonomer needed toachieve this result will depend on the particular comonomer(s) beingemployed, the catalyst composition, and, particularly, the molar ratioof aluminum to chromium, catalyst preparation conditions, and reactortemperature. The ratio of the comonomer to ethylene is controlled toobtain the desired resin density of copolymer product.

The conditions for polymerizations vary depending upon the monomers,catalysts and equipment availability. The specific conditions are knownor readily derivable by those skilled in the art. In some embodiments ofthis disclosure, polyolefins produced may include those made from olefinmonomers such as ethylene and linear or branched higher alpha-olefinmonomers containing 3 to about 20 carbon atoms. In other embodiments,homopolymers or interpolymers of ethylene and these higher alpha-olefinmonomers, with densities ranging from about 0.905 g/cc to about 0.97g/cc, may be made; densities ranging from about 0.915 to about 0.965 inother embodiments. Exemplary higher alpha-olefin monomers may include,for example, propylene, 1-butene, 1-pentene, 1-hexene,4-methyl-1-pentene, 1-octene, and 3,5,5-trimethyl-1-hexene. Exemplarypolyolefins may include ethylene-based polymers (at least 50 mole %ethylene), including ethylene-1-butene, ethylene-1-hexene, andethylene-1-octene copolymers, such as high density polyethylene (HDPE),medium density polyethylene (MDPE) (including ethylene-butene copolymersand ethylene-hexene copolymers), low density polyethylene (LDPE), linearlow density polyethylene (LLDPE), or homopolyethylene.

In certain embodiments, polymers of the present disclosure may have flowindices (I21) ranging from about 0.1 g/10 min to about 1000 g/10 min. Inother embodiments, polymers of the present disclosure may have flowindices (I21) ranging from about 1 g/10 min to about 300 g/10 min. Inyet other embodiments, polymers of the present disclosure may have flowindices (I21) ranging from about 0.5 g/10 min to about 60 g/10 min.

In some exemplary embodiments, the processes and catalysts disclosedherein may be used to produce polyolefins such as ethylene/1-hexenecopolymer or ethylene homopolymer under specific reactor conditions. Forexample, the H2/C2 gas molar ratio may be in the range of from about0.01 to about 0.5. Oxygen add back may be in the range of from about 10to about 600 ppbv relative to the ethylene feed rate to the reactor. Thereactor operating temperature may be in the range of from about 75 toabout 120° C. The reactor may be optionally run in the condensing mode.The conditions for polymerizations vary depending upon the monomers,catalysts and equipment availability. The specific conditions are knownor readily derivable by those skilled in the art.

The following test methods should be utilized to obtain the numericalvalues for certain properties and features as disclosed, e.g. density,productivity, chromium content, or flow indices or melt indices,although it is understood that those values also refer to any resultsobtained by other testing or measuring methods that might notnecessarily be disclosed herein, provided such other testing ormeasuring methods are published, e.g., in at least one patent, patentapplication, or scientific publication. Also, it is understood that thevalues set forth in the claims may have some degree of error associatedwith their measurement, whether experimental, equipment, or operatorerror; and that any value in the claim is approximate only, andencompasses values that are plus or minus (+/−)10% or even 20% from themeasured value.

Density values are based on ASTM D1505. Flow Index (I21) values arebased on ASTM D1238, run at 190° C., with 21.6 kg weight; the standarddesignation for that measurement is 190/21.60. Melt Index (I5) valuesare based on ASTM D1238, run at 190° C., with 5.0 kg weight; thestandard designation for that measurement is 190/5. Melt Index (I2)values are based on ASTM D1238, run at 190° C., with 2.16 kg weight; thestandard designation for that measurement is 190/2.16.

The discussion herein illustrates, among other things, for reducedchromium oxide catalysts and reduced silyl chromate catalysts the effecton flow index response of using differing reducing agent addition timesand different agitation rates, and surprisingly different dryingtemperatures, in both a fluidized-bed gas phase polymerization processand in a slurry polymerization process, for polyethylene copolymers,which included ethylene units as well as other monomeric units. Theseeffects may be utilized to tailor the flow index response of a catalystso as to make target polymers with high, medium, or low flow indicesunder a variety of polymerization conditions.

As described above, the flow index response of a chromium-based catalystcan be tailored by contacting the chromium-based catalyst with areducing agent fed at a selected feed rate over a selected time periodand optionally at a selected agitation rate, and subsequently dried atan adjustable specified drying temperature (at a specified drying time).The use of the chromium-based catalyst compositions described herein,wherein the catalysts have a tailored or selected flow index response,provides a capacity for polymerization process flexibility, which hassignificant commercial application in the polymerization of polyolefins.

In addition, embodiments of the present disclosure provide a process forproducing chromium-based catalyst compositions with a selected flowindex response. Yet other embodiments provide a process for producingpolyolefins comprising forming a chromium-based catalyst compositionwith a selected flow index response, as described herein, and contactingthe chromium-based catalyst composition with olefins underpolymerization conditions.

Advantageously, embodiments disclosed herein provide for a method totailor the flow index response of chromium-based catalysts. The abilityto select the flow index response of a chromium-based catalyst furtheradvantageously allows for a greater number of polymerization products tobe produced with chromium-based catalysts than was previously possible.Additionally, chromium-based catalysts having a low or moderate flowindex response advantageously allow lower flow index products to bemanufactured with chromium-based catalysts at significantly higherreactor temperatures, where cooling is more efficient and higherproduction rates may be achieved. As another advantage, chromium-basedcatalysts having a higher flow index response result in lower hydrogenfeed rates to the reactor. Chromium-based catalysts having a higher flowindex response can also result in lower oxygen addback feed rates to thereactor which correlate with improved catalyst productivity and higherfluidized bulk density of the polyethylene particles which can lead tohigher polyethylene production rate for a given equipment size. As yetanother advantage, the greater flexibility for chromium-based catalyststo produce polymers of varying flow indices allows for improved gradetransitions.

Inline Reduction of Chromium-Based Catalysts for Polyolefin Production

The polymerization reactor systems discussed in the above section“Polymerization Processes” and other polymerization reactor systems mayemploy an inline reduction of chromium-based catalyst, as discussedbelow with respect to FIGS. 10 and 11. Indeed, in lieu of employing theaforementioned upstream mix vessel to reduce and isolate charges ofchromium-based catalyst, the chromium-based catalyst may instead bereduced inline (with a reducing agent) as feed to one or more of thepolyolefin polymerization reactors discussed above in the section“Polymerization Processes.” In certain embodiments, the inline reductionmay be part of the polymerization reactor system or its feed system. Theinline reduction may be performed without solvent removal and, thus, astream of the chromium-based catalyst, solvent, and any remainingreducing agent may enter the polymerization reactor.

Advantageously, embodiments of the present inline reduction may avoid adrop (e.g., of 4 lb/ft3) in polymer bulk density values associated withconventional in-situ reduction of the chromium-based catalyst withreducing agent introduced directly to the polymerization reactor andfirst contacting the chromium-based catalyst in the polymerizationreactor. Further, in some examples, the amount of reducing agentutilized may be beneficially decreased with the inline reduction, ascompared to the aforementioned reduction of chromium-based catalyst in abatch mix vessel in an upstream step. In other words, for the samecatalyst grade or type subjected to the same amount of reducing agent(i.e., the same reducing agent/Cr ratio), a greater flow index responseof the chromium-based catalyst may be realized with inline reductionversus the drying and isolation of reduced chromium-based catalyst witha mix vessel 102, for instance. In some cases as discussed below, theflow index response increases significantly for inline reduction ofcatalyst versus batch reduced and dried isolated catalyst at the samereducing agent/Cr ratio.

Furthermore, as discussed below, the inline reduction may alsobeneficially facilitate substantially real-time control of productproperties (e.g., flow index) of the product polyolefin via adjustingthe addition rate of reducing agent in the inline reduction. The presentinline reduction may include an inline static mixer, an inline agitatorvessel, an inline stirred vessel, or the like. The mixer, static mixer,agitated vessel, stirred vessel, and/or conduit volume may provide for aspecified residence time of contact of the chromium-based catalyst withthe reducing agent.

FIG. 10 is a polymerization reactor system 1000 having an inlinereduction system 1002 for mixing a reducing agent 1004 with asubstantially continuous feed of chromium-based catalyst 1006. Thereduction system 1002 includes an inline mixer 1008 to mix the reducingagent 1004 with the chromium-based catalyst 1006 in route to apolymerization reactor 1010. The polymerization reactor 1010 polymerizesan olefin into a polyolefin in the presence of the chromium-basedcatalyst 1006.

The polymerization reactor 1010 may be a liquid phase reactor, such as aloop reactor, a boiling liquid-pool reactor, an autoclave reactor, andthe like. The polymerization reactor 1010 may also be a gas phasereactor such as fluidized bed, horizontal-stirred, or vertical stirred,reactors, and so forth. Again, the reactor 1010 may be one of thereactor types discussed above in the section entitled “PolymerizationProcesses.” Moreover, the reactor system 1000 may generally includeequipment and subsystems associated with the reactor 1010, as discussedabove. The reactor 1010 may represent more than one reactor disposed inseries and/or parallel.

The chromium-based catalyst 1006 received at the mixer 1008 and flowingthrough the mixer 1008 may be of the aforementioned chromium-basedcatalyst types discussed throughout the present disclosure. The catalyst1006 may be chromium oxide catalysts and/or silyl chromate catalysts,for example. The chromium-based catalyst 1006 may be supported, and maybe activated such as in an upstream activation system where an oxidationstate of chromium in the catalyst 1006 is increased from +3 to +6, forinstance. The chromium-based catalyst 1006 may be received at the mixer1008 as a substantially dry catalyst if feasible, but is insteadtypically received in a slurry with an alkane solvent, mineral oil, andthe like. The amount or rate of the catalyst 1006 to the mixer (andultimately to the reactor 1010) may be controlled and modulated to givea desired production rate of polyolefin in the polymerization reactor1010, a desired grade of polyolefin and polyolefin property values, thelike.

The reducing agent 1004 may be an organoaluminum compound (e.g., DEAlE)and may be diluted in an inert solvent such as an alkane. The additionrate of the reducing agent 1004 may be modulated with a control valve1012 such as a flow control valve. Indeed, as discussed below, theaddition flow rate of the reducing agent 1004 may be an operatingvariable of the polymerization reactor system 1000 to give a desiredflow index (and other desired properties) of the polyolefin productdischarging from the polymerization reactor 1010. The reducing agent1004 (with solvent) may be added to the catalyst 1006 near or at theentrance of the mixer 1008, as depicted, or may be added directly to themixer 1008.

In certain embodiments, the mixer 1008 is a static mixer or a pluralityof static mixers disposed in series and/or parallel. The mixer 1008 mayalso be or include a stirred or agitated vessel in lieu of or inaddition to a static mixer(s). If so, the speed of agitation in themixer(s) 1008 may be adjusted to give good mixing and/or to change themixing characteristics in response to change in operating conditions ofthe polymerization reactor. Such changes in operating conditions of thepolymerization reactor may include changes in flow index response and/orchanges in the polymer resin average particle size distribution such asincrease in the resin fines fraction, and so on. The mixer 1008 may alsobe a plurality of agitated vessels. Moreover, the inline mixer 1008 maybe other types of mixers, and generally is a unit operation to providefor contact and mixing of the reducing agent 1004 with thechromium-based catalyst 1006. The mixer 1008 may be configured and sizedbased on typical flow rates of the catalyst 1006 and the reducing agent1004 to give particular residence times of the contact/mixing andreaction of the reducing agent 1004 with the chromium-based catalyst1006 in the mixer 1008. In certain embodiments, the contact residence ofthe mixer 1008 is in exemplary ranges of about 2 minutes to 120 minutes,about 18 minutes to 30 minutes, and so on. Other contact residence timeranges are applicable. The contact residence time of the mixer 1008 maybe considered the residence time of the contact of the catalyst 1006with the reducing agent 1004 through the mixer 1008. Additional contactresidence time of the catalyst 1006 with the reducing agent 1004 may becontributed by piping or tubing between the mixer 1008 and thepolymerization reactor 1010. The contact residence time may affect theflow index response of the catalyst and, thus, the flow index of thepolymer in the downstream polymerization reactor. Indeed, differences inflow index response of the catalyst have been observed, for example,between contact residence times of about 20 minutes and about 80minutes.

The operating temperature of the mixer 1008 may be ambient in someexamples. Thus, the reduction of the catalyst 1006 in the mixer 1008 mayoccur at ambient temperature. In other embodiments, the mixer operatingtemperature 1006 may be increased above ambient, such as via heating ofthe incoming streams 1004 and 1006, as well as heating of the mixer1008. Cooling may also be employed to maintain a desired operatingtemperature of the mixer 1008 and to remove the heat of the reaction ofthe reducing agent with the chromium-based catalyst. The operatingpressure of the mixer 1008 may be a function of flowing supply pressureof the incoming streams 1004 and 1006, the backpressure of thepolymerization reactor 1010, and so forth. Moreover, pressure control atthe mixer 1008 may be implemented in alternate embodiments.

The chromium-based catalyst composition 1014 discharging from the mixer1008 generally includes the chromium-based catalyst 1006 (some of whichmay have been reduced in the mixer 1008), solvent, and any remainingreducing agent 1004. The catalyst composition 1014 substantiallycontinuously flows as feed to the polymerization reactor 1010. Reductionof the chromium-based catalyst 1006 occurs in the mixer 1008. Suchreduction may also continue to occur in the chromium-based catalystcomposition 1014 in the feed piping or tubing from the mixer 1008 to thereactor 1010, and in the reactor 1010 in certain embodiments. Thereduction may involve reducing at least some of the chromium sites froman oxidation state of +6 to +3 and/or +2, for example. In certainembodiments, chromium-based catalyst 1006 entering the inline reductionsystem 1002 is not previously contacted with a reducing agent. In otherembodiments, the chromium-based catalyst 1006 entering the inlinereduction system 1002 is previously contacted with a reducing agent, andadditional reduction may occur via the inline reduction system 1002.

Additional feed components, as discussed above in the section“Polymerization Processes” and as represented by a single arrow 1016 inFIG. 10, are fed to the polymerization reactor. Such feed components mayinclude olefin, comonomer, hydrogen, additives, and other components. Inthe reactor 1010, the olefin, and any comonomer, is polymerized topolyolefin in the presence of the catalyst composition 1014 and anyhydrogen and/or additives. A product polyolefin 1018 stream dischargesfrom the polymerization reactor 1010.

In embodiments, the olefin is ethylene, the comonomer is 1-butene or1-hexene, and the product polyolefin 1018 is polyethylene. In otherembodiments, the olefin is propylene, the comonomer if employed isethylene, and the product polyolefin is polypropylene. As mentioned, thepolymerization reactor 1010 typically includes associated equipment andsubsystems in the reactor system 1000. Furthermore, the productpolyolefin 1018 stream may be further processed, combined withadditives, and the polyolefin 1018 extruded into pellets, for example,for distribution to customers or end-users.

The addition rates of feed components and the operating conditions(e.g., pressure, temperature) of the reactor 1010 may be controlled togive a desired polymerization mixture or recipe in the reactor 1010 andthus the desired grade and properties of the product polyolefin 1016.Such control may generally impact the productivity of the catalyst 1006or catalyst composition 1014, the production rate of the productpolyolefin 1018, and so on. In accordance with embodiments of thepresent techniques, the addition rate of the reducing agent 1004 to theinline reduction system 1002 may be an additional operating variable ofthe reactor system 1000 to facilitate control of properties, e.g., flowindex, density, etc., of the product polyolefin 1018, as well asproductivity of the catalyst 1006, the production rate of the polyolefin1018, and the like.

As mentioned, the addition or flow rate of the reducing agent 1004 tothe mixer 1008 may be modulated by a control valve 1012. The modulationand control of the flow rate of the reducing agent 1004 via the controlvalve 1012 may be under the direction of a control system 1020, whichmay be analogous to the aforementioned control system 116. A flowcontrol loop in a DCS control system 1020 may direct operation (valveposition) of the control valve 1012 to give the desired flow rate or theset-point flow rate of the reducing agent 1004 to the mixer 1008.

The addition or feed rate, e.g., in mass per time or volume per time, ofthe reducing agent 1004 may be manipulated by the control valve 1012under the direction of the control system 1020 or other control system.A set point of the feed rate may be specified in the control system 1020based on, or in response to, the desired flow index or other property ofthe product polyolefin 1018. The set point of the feed rate of thereducing agent 1004 may also be specified in the control system 1020 towork in concert with other operating variables to give certain catalystproductivity values, production rates of the polyolefin 1018, and otheroperating conditions of the reactor 1010 and reactor system 1000.

A flow sensor 1022, such as a mass meter, flow measure orifice (e.g.,with differential pressure taps), and so on, may measure the flow rateof the reducing agent 1004, and indicate such measured flow rate valuesto the control system 1020. A transmitter may send a signal to thecontrol system 1020 indicating the measured flow rate. This flow controlloop implemented via the control system 1020, e.g., as a control blockin a DCS control system 1020, may adjust the valve opening position ofthe control valve 1012 to maintain the flow rate of reducing agent 1004at set point, i.e., the desired addition rate of reducing agent 1004 tothe inline reduction system 1002 and its mixer 1008.

Lastly, a solvent 1024 may be added to the mixer 1008 to adjust theresidence time or contact residence time of the chromium-based catalystthrough the mixer 1008. The solvent 1024 may be added directly to themixer 1008, to a conduit supplying the catalyst 1006 to the mixer 1008,to a conduit supplying the reducing agent 1004 to the mixer 1008, andthe like. In the illustrated embodiment, the addition rate of thesolvent 1024 may be modulated with a control valve 1026 which mayoperate under the direction of the control system 1020.

FIG. 11 is a method 1100 of operating a polyolefin reactor system. Themethod includes feeding a chromium-based catalyst, as indicated in block1102, through an inline reduction system to a polymerization reactor.This catalyst feed may be a substantially continuous feed through theinline reduction system to the polymerization reactor. The inlinereduction system may have a mixer that contacts the chromium-basedcatalyst with a reducing agent. The mixer may be an inline mixerincluding a static mixer, an agitator vessel, a stirred vessel, and soon.

A reducing agent is added (block 1104) to the chromium-based catalyst inthe inline reduction system to reduce an oxidation state of at least aportion of the chromium in the chromium-based catalyst. The reducingagent may be added to the chromium-based catalyst at the mixer orupstream of the mixer, or a combination thereof. The reducing agent maybe an organoaluminum compound (e.g., DEAlE and/or TEAL) and may bediluted in a solvent such as an alkane solvent.

Further, a solvent may be added (block 1106) to the inline reductionsystem to adjust a residence time or contact residence time of thechromium-based catalyst and the reducing agent in the mixer. Anexemplary contact residence time of the chromium-based catalyst in themixer may be in the range of about 2 minutes to about 120 minutes, inthe range of about 18 minutes to about 30 minutes, and so forth.

At block 1108, an olefin, or a mixture of olefins, is polymerized into apolyolefin in the polymerization reactor in presence of thechromium-based catalyst fed through the inline reduction system to thepolymerization reactor. In certain embodiments, the olefin is ethyleneand the polyolefin is polyethylene. The polymerization reactor may be agas phase reactor and/or liquid-phase reactor.

At block 1110, the addition rate or flow rate of the reducing agent tothe inline reduction system and its mixer may be specified and adjustedto give a desired flow index of the polyolefin produced in thepolymerization reactor. The adjustment of the reducing agent additionrate may be in response to a measured flow index of the polyolefin.Indeed, the method 1100 may include adjusting a flow index of thepolyolefin by modulating the addition rate of the reducing agent to thechromium-based catalyst. Further, the addition rate of the reducingagent to the chromium-based catalyst may be adjusted in response tooperating conditions of the polymerization reactor. In some cases tocontrol the flow index, the addition rate of the reducing agent may bebased on achieving or changing a target added aluminum concentration onthe reduced catalyst. In some cases to control the flow index, theaddition rate of the reducing agent may be based on achieving orchanging a target added aluminum to chromium molar ratio on the reducedcatalyst. The addition rate of the reducing agent may further beadjusted to maintain a target feed ratio relative to the catalyst feedrate or changes in the catalyst feed rate as may be beneficial, forexample, to manipulate the polymer production rate of the downstreampolymerization reactor.

In sum, an embodiment provides a method of operating a polyolefinreactor system, the method including feeding a chromium-based catalyst(e.g., chromium oxide catalyst) through an inline reduction system to apolymerization reactor such as a gas phase reactor. The chromium-basedcatalyst may be fed substantially continuously through the inlinereduction system to the polymerization reactor. The method includesadding a reducing agent to the chromium-based catalyst in the inlinereduction system to reduce an oxidation state of at least a portion ofthe chromium in the chromium-based catalyst, and polymerizing an olefin(e.g., ethylene) into a polyolefin (e.g., polyethylene) in thepolymerization reactor in presence of the chromium-based catalyst. Thereducing agent may include an organoaluminum compound, an organoaluminumcompound diluted in a solvent, and so forth. In particular examples, thereducing agent may include DEAlE, TEAL, both DEAlE and TEAL, and so on.The inline reduction system may include a mixer such as a static mixeror stirred vessel that contacts the chromium-based catalyst and thereducing agent.

Furthermore, the method may include adding solvent to the inlinereduction system to adjust contact residence time of the chromium-basedcatalyst and the reducing agent in the mixer. The addition rate ofsolvent to the inline reduction system may be adjusted in response tooperating conditions of the polymerization reactor, in response to ameasured flow index of the polyolefin, to maintain a flow index of thepolyolefin, or to give a different flow index of the polyolefin. Theaddition rate of solvent to the mixer may be adjusted in response to achange in a feed rate of the chromium-based catalyst, to maintain asubstantially constant a residence time of the chromium-based catalystthrough the mixer, or to alter the contact residence time.

The method may include specifying the addition rate of the reducingagent to the inline reduction system to give the desired flow index ofthe polyolefin. Similarly, the method may include specifying the ratioof the addition rate of the reducing agent to the feed rate of thechromium-based catalyst through the inline reduction system to give thedesired flow index of the polyolefin. The method may include adjustingthe addition rate of the reducing agent to the inline reduction systemin response to the measured flow index of the polyolefin. Likewise, themethod may include adjusting the ratio of addition rate of the reducingagent to feed rate of the chromium-based catalyst through the inlinereduction system in response to the measured flow index of thepolyolefin. The method may include adjusting the aluminum concentrationon the chromium-based catalyst to give a desired flow index of thepolyolefin, and/or specifying the aluminum to chromium molar ratio onthe chromium-based catalyst to give the desired flow index of thepolyolefin. Moreover, the method may include adjusting the aluminum tochromium molar ratio or an aluminum concentration on the chromium-basedcatalyst in response to changes in a feed rate of the chromium-basedcatalyst to maintain the desired flow index of the polyolefin. Themethod may include adjusting a ratio of feed rate of the reducing agentto feed rate of the chromium-based catalyst through the inline reductionsystem to maintain a flow index value of the polyolefin.

The method may or may not include contacting the chromium-based catalystwith additional reducing agent in another system prior to feeding thechromium-based catalyst through the inline reduction system. Thus, incertain embodiments, the chromium-based catalyst is not contacted withreducing agent prior to feeding the catalyst through the inlinereduction system. On the other hand, in other embodiments, thechromium-based catalyst is contacted with reducing agent prior tofeeding the chromium-based catalyst through the inline reduction system.

Another embodiment provides a method of operating a polyolefin reactorsystem, including feeding a chromium-based catalyst through an inlinemixer to a polymerization reactor, adding a reducing agent to contactthe chromium-based catalyst through the inline mixer to thepolymerization reactor, and polymerizing an olefin into a polyolefin inthe polymerization reactor in presence of the chromium-based catalyst.The chromium-based catalyst may be fed as a slurry through the inlinemixer to the polymerization reactor. The reducing agent may be added tothe chromium-based catalyst at the mixer or upstream of the mixer, or acombination thereof. The method may include modulating the addition rateof the reducing agent to the chromium-based catalyst. Indeed, thereducing agent may be added to the chromium-based catalyst at aspecified flow rate to give a desired flow index of the polyolefin. Forinstance, adding the reducing agent may involve adjusting the additionrate of the reducing agent to maintain a desired ratio of the additionrate of the reducing agent to a feed rate of the chromium-based catalystthrough the mixer. The method may include adjusting the ratio of feedrate of the reducing agent to feed rate of the chromium-based catalystthrough the mixer to give a desired flow index of the polyolefin. Themethod may include adjusting the addition rate of the reducing agent tothe chromium-based catalyst in response to operating conditions of thepolymerization reactor. Also, the method may include adjusting theagitation speed of an agitator of the inline mixer in response tooperating conditions of the polymerization reactor. Further, the methodmay include adjusting a molar ratio of the reducing agent to thechromium-based catalyst in response to operating conditions of thepolymerization reactor. The method may include adjusting the feed rateof the reducing agent to the chromium-based catalyst to maintain aspecified molar ratio of the reducing agent to the chromium-basedcatalyst through the mixer to give the desired flow index of thepolyolefin.

Solvent may be added to the chromium-based catalyst through the inlinemixer to maintain or adjust a contact residence time of thechromium-based catalyst and the reducing agent. Exemplary contactresidence times of the chromium-based catalyst and reducing agent in theinline mixer may be in the range of 2 minutes to 120 minutes, in therange of 18 minutes to 30 minutes, and so forth. The method may includeadjusting the addition rate of solvent to the mixer in response tooperating conditions of the polymerization reactor or in response to themeasured flow index of the polyolefin. The method may include adjustingaddition rate of solvent to the mixer in response to a change in feedrate of the chromium-based catalyst and to maintain a residence time ofthe chromium-based catalyst through the mixer.

Lastly, an embodiment of a polymerization reactor system includes amixer (e.g., static mixer or stirred vessel) to contact a substantiallycontinuous feed of chromium-based catalyst to a polymerization reactorwith a reducing agent to form a catalyst feed composition having thechromium-based catalyst in route to the polymerization reactor. Aresidence time of the chromium-based catalyst through the mixer may bein the range of 2 minutes to 120 minutes in certain examples, or in therange of 18 minutes to 30 minutes in other examples. The reactor systemincludes a polymerization reactor (e.g., a gas phase reactor) thatreceives the catalyst feed composition and in which an olefin ispolymerized into a polyolefin in presence of the chromium-basedcatalyst. The reactor system includes a control system to adjust theaddition rate of the reducing agent to the mixer to give a desired flowindex of the polyolefin. The control system may utilize a control valveto modulate the addition rate, e.g., a flow rate or feed rate in massper time or volume per time, of the reducing agent to the inlinereduction system having the mixer.

In addition, embodiments of the present disclosure provide a process forproducing chromium-based catalyst compositions with a selected flowindex response. Yet other embodiments provide a process for producingpolyolefins comprising forming a chromium-based catalyst compositionwith a selected flow index response, as described herein, and contactingthe chromium-based catalyst composition with olefins underpolymerization conditions.

Advantageously, embodiments disclosed herein provide for a method totailor the flow index response of chromium-based catalysts. The abilityto select the flow index response of a chromium-based catalyst furtheradvantageously allows for a greater number of polymerization products tobe produced with chromium-based catalysts than was previously possible.Additionally, chromium-based catalysts having a low or moderate flowindex response advantageously allow lower flow index products to bemanufactured with chromium-based catalysts at significantly higherreactor temperatures, where cooling is more efficient and higherproduction rates may be achieved. As another advantage, chromium-basedcatalysts having a selected flow index response result in lower hydrogenfeed rates to the reactor. As yet another advantage, the greaterflexibility for chromium-based catalysts to produce polymers of varyingflow indices allows for improved grade transitions.

For the sake of brevity, only certain ranges are explicitly disclosedherein. However, ranges from any lower limit may be combined with anyupper limit to recite a range not explicitly recited, as well as, rangesfrom any lower limit may be combined with any other lower limit torecite a range not explicitly recited, in the same way, ranges from anyupper limit may be combined with any other upper limit to recite a rangenot explicitly recited. Additionally, within a range includes everypoint or individual value between its end points even though notexplicitly recited. Thus, every point or individual value may serve asits own lower or upper limit combined with any other point or individualvalue or any other lower or upper limit, to recite a range notexplicitly recited.

All priority documents are herein fully incorporated by reference forall jurisdictions in which such incorporation is permitted and to theextent such disclosure is consistent with the description of the presentinvention. Further, all documents and references cited herein, includingtesting procedures, publications, patents, journal articles, etc. areherein fully incorporated by reference for all jurisdictions in whichsuch incorporation is permitted and to the extent such disclosure isconsistent with the description of the present invention.

While the invention has been described with respect to a number ofembodiments and examples, those skilled in the art, having benefit ofthis disclosure, will appreciate that other embodiments can be devisedwhich do not depart from the scope and spirit of the invention asdisclosed herein.

EXAMPLE SECTION

It is to be understood that while the invention has been described inconjunction with the specific embodiments thereof, the foregoingdescription is intended to illustrate and not limit the scope of theinvention. Other aspects, advantages and modifications will be apparentto those skilled in the art to which the invention pertains.

Therefore, the following Examples are put forth so as to provide thoseskilled in the art with a complete disclosure and description of how tomake and use the compounds of the invention, and are not intended tolimit the scope of that which the inventors regard as their invention.

High-density polyethylene resin samples were prepared in polymerizationsusing catalysts made employing different locations and arrangements onthe mix vessel for reducing agent feed introduction, different dryingline-out temperatures and times, different batch sizes, and in somecases by inline reduction, as noted in Tables 1 through 6 below. Theexamples in Tables 1 and 5 are chromium oxide catalysts reduced oneither a pilot scale or a commercial plant scale. For some of thesecatalysts, the Table 1 includes laboratory-scale slurry polymerizationreactor results. The examples in Table 2 are chromium oxide catalystsmade on a pilot plant scale and used to polymerize olefin in apilot-plant gas-phase (fluidized-bed) polymerization reactor. Theexamples in Tables 3 and 6 are chromium oxide catalysts made on a plantscale and polymerized in a gas-phase, fluidized-bed polymerization pilotreactor. These examples collectively illustrate the controlling ortailoring of the flow index response of a catalyst by using differentDEAlE feed arrangements and selected drying line-out temperatures forselected drying times, and different batch sizes. The examples in Table4 are chromium oxide catalysts activated on a plant scale and used topolymerize olefin in a pilot-plant gas-phase (fluidized-bed)polymerization reactor by means of inline reduction with reducing agent.

General Catalyst Preparation (Chromium Oxide Catalysts)

Catalysts employed in the Examples were activated on a commercial scaleas follows. A suitable quantity of a porous silica support containingabout 5 weight percent chromium acetate (Grade C35300MSF chromium onsilica, produced by PQ Corporation), which amounts to about 1 weightpercent Cr content, having a particle size of about 82 microns and asurface area of about 500 square meters per gram was charged to afluidized bed heating vessel. There, the catalyst precursor (chromium onsilica) was heated slowly at a rate of about 50° C. per hour under drynitrogen up to 200° C. and held at that temperature for about 4 hours.Next, the chromium on silica was heated slowly at a rate of about 50° C.per hour under dry nitrogen up to 450° C. and held at that temperaturefor about 2 hours. The nitrogen stream was then replaced with a streamof dry air and the chromium on silica was heated slowly at a rate ofabout 50° C. per hour to 600° C. where it was activated for about 6hours. The activated catalyst was then cooled with dry air (at ambienttemperature) to about 300° C. and further cooled from 300° C. to roomtemperature with dry nitrogen (at ambient temperature). The resultingcooled catalyst powder was stored under nitrogen atmosphere untiltreated with a reducing agent in a mix vessel or by means of inlinereduction as described below.

In a typical chromium oxide catalyst reduction, the catalyst was placedin a vertical catalyst blender with a double helical ribbon agitatorunder an inert atmosphere. Dried hexane or isopentane solvent was addedto adequately suspend the supported catalyst. All catalysts usedC35300MSF starting material in the Examples listed in Tables 1, 2, 3, 5,and 6. Catalyst batch size was varied in the Examples made and used inTables 5 and 6. For all of these catalysts, about 7.1 liters of solventwere charged per kilogram (0.89 gallons per pound) of support. DEAlE,available from Akzo Nobel, and obtained as a 25 wt % solution inisopentane or hexane, was then added above the surface of the catalystslurry at a selected rate over about a 40 minute time period to obtain aselected weight percent aluminum loading on the catalyst. The DEAlE feedlocation was varied radially from the center vertical axis of thevessel. DEAlE insert tubes were either absent or were used with varyingtube length below the underside of the top head of the vessel. Themixture was agitated at a selected agitation rate at a temperature ofapproximately 45° C. during the addition time. The mixture was furtheragitated at a controlled rate for about 1 hour on a pilot scale or 2hours on a commercial scale. Then the solvent was substantially removedby drying at a selected jacket temperature for about 16 to 21 hours. Thejacket temperature was selected to give a material temperature thatlined out near the target of 61, 64, 71, or 81° C. during the laterhours of drying. Pilot-scale C35300MSF-based catalysts were generallydried for 16 hours total with progressively stronger vacuum beingapplied as drying time increased. Example 9 was dried for 19 hourstotal. Plant-scale C35300MSF-based batches were dried for 18 or 21 hourstotal at slightly above atmospheric pressure. The only plant-reducedcatalysts in these examples that were dried for 18 hours total were inComparative Examples 10, 25, and 26. The drying time total is the ramptime and line-out time. The “drying line-out time” is the time while thebed temperature was within 2° C. of the final line-out temperature, andranged from about 6 to about 11 hours in most of these Examples. Theresulting dry, free flowing catalyst powder was then stored undernitrogen until used.

General Laboratory Testing Procedures for Catalysts

Certain catalyst samples that were prepared as described above and shownin Table 1 were tested for their flow index response in a laboratory1-liter slurry reactor. In a typical slurry polymerization, catalyst wascharged to a reactor equipped with a mechanical stirrer and a jacket forinternal temperature control. In Examples 8 and 9, an amount of 0.144 to0.146 g of catalyst was introduced. In the remaining Examples given inTable 1, an amount of 0.177 to 0.210 g of catalyst was introduced. Thiswas followed by 600 mL of dry purified isobutene, and 500 cc of hydrogenwas batch charged, the reactor was brought up to reaction temperature(95° C. in these examples), during which step ethylene feed was started,and 10 mL of 1-hexene was batch charged through a small gas cylinder.The ethylene was fed continuously upon demand to maintain an ethylenepartial pressure of 13.8 bar (200 psi). Ethylene uptake was measuredwith an electronic flow meter. Polymerizations were run until about 180grams of polyethylene were made. The reactor was opened afterdepressurization and cooled in order to recover the polymer. Afterdrying, polymer flow index was measured.

General Pilot Plant Testing Procedure for Reduced and Dried Catalysts

Certain catalyst samples that were prepared as described above and shownin Tables 2, 3, and 6 were tested for their flow index response makingethylene/1-hexene copolymer product in a 14-inch diameter pilot-scalefluidized-bed reactor. Cycle gas was circulated through the reactor andheat of reaction was removed in a heat exchanger. Catalyst powder wascontinuously introduced into the fluidized bed. Monomers, hydrogen andoxygen were fed into the cycle gas piping. Product was transferredintermittently into a product chamber, depressurized, degassed briefly,and then discharged into a drum. Conditions in the fluidized-bed reactorwere maintained at a constant value or in a narrow range for the relatedexperiments within each set of tests that were conducted. Reactor bedtemperature was about 98.2° C. Ethylene partial pressure was about 13.8bar (200 psi). The H2/C2 molar gas ratio in the cycle gas was maintainedat about 0.04. The 1-hexene to ethylene molar ratio in the cycle gas wasmaintained at about 0.0100. The oxygen added to ethylene in the feed gaswas maintained at about 25 ppb by volume. Total reactor pressure wasabout 24.8 bar absolute (360 psia). Superficial gas velocity within thefluidized bed was 1.78-1.93 ft/s. Average residence time of resin in thereactor ranged from 2.08 to 2.28 hours. Tables 2, 3, and 6 summarize thecatalyst information and reaction conditions along with the resultingpolymer properties.

Examples 1, 2, 4, 5, 6, and 7

In Examples 1, 2, 4, 5, 6, and 7, DEAlE-reduced chromium oxide-basedcatalysts were prepared on a pilot scale using plant-activated C35300MSFsupport as described above and then tested for flow index response in alaboratory slurry polymerization reactor. Catalyst preparationconditions used are indicated in Table 1 (agitation rate during DEAlEaddition and reaction, wt % Al loading, DEAlE addition time, DEAlE feedarrangement, and drying line out temperature and time). Batch sizes wereabout 88% full where full in the Examples refers to a batch size thatjust reaches the top of the agitator impeller blades. Laboratory slurrypolymerization results are shown in Table 1 and in FIGS. 4 and 6.

The results show that at an agitation rate within a narrow range, andwithin a narrow range of wt % Al loading, and within a narrow range ofDEAlE addition time, the measured flow index response increased when theDEAlE was fed with an insert tube to substantially prevent it fromrunning down the underside of the vessel head over to the vessel wall.The results also show the measured flow index response increased furtherwhen the tube tip was located further from the wall, which meant moretowards the center of the vessel.

Comparative Examples 1 and 2 show the relatively low measured flowindices (20 and 35 dg/min) obtained for polymer from two lab slurrypolymerizations with pilot-plant reduced catalyst, made without aninsert tube and with the DEAlE added about 90% of the distance radiallyfrom the vertical center line of the vessel, so at a position very nearthe wall. During these catalyst preparations the DEAlE was observedflowing entirely or nearly entirely along the underside of the head anddown the side wall where it contacted a green viscous agglomeration thatwas observed to have formed within 20 minutes of starting DEAlE additionand moved more slowly than the bulk of the reaction slurry. Examples 5and 7 in comparison with Examples 1 and 2 show that when an insert tubeof at least 0.5 inch protrusion below the top head was used, at alocation about 83% of the radial distance from the vertical centerlineof the vessel, the measured flow index increased significantly to 76dg/min, and it increased further to 104 when an insert with 1-inchprotrusion was used at a location about 67% of the radial distance fromthe vertical centerline of the vessel. FIG. 4 displays this effect in abar chart. The drying line-out temperature was 70 to 72° C. in thesefour examples. Examples 4 to 6 show that when drying line outtemperature was reduced from the region of 72 to 82° C. down to about61° C., the measured flow index significantly increased, from about 76to about 101 dg/min. FIG. 6 displays this effect graphically. As shownby the examples above, it is possible to tailor the flow index responseof pilot-scale DEAlE-reduced activated C35300MSF-based chromium oxidecatalysts by varying the DEAlE feed location radially, by using a DEAlEfeed tube insert protruding below the underside of the top head of thevessel, and/or by varying the catalyst drying line out temperature andtime.

Examples 8 and 9

In Examples 8 and 9, DEAlE-reduced chromium oxide-based catalysts werereduced on a pilot plant scale using plant-activated C35300MSF supportas described above. Catalyst preparation conditions used are indicatedin Table 1 (agitation rate during DEAlE addition and reaction, wt % Alloading, DEAlE addition time, DEAlE feed arrangement, and drying lineout temperature and time). Batch sizes were about 88% full where fullrefers to a batch size that just reaches the top of the agitatorimpeller blades. Examples 4 through 6 showed the improved flow indexresponse possible by drying at lower line out temperature. In order toreach the same level of residual solvent in the final catalyst,extending the drying time is one option. In Examples 8 and 9, todetermine any deleterious effects of increased drying time on catalystperformance, catalyst was dried differently than in other examples.Catalyst in Example 8 was dried for 16 total hours, but catalyst inExample 9 was dried for 19 total hours. In both of these examplesgentler vacuum was applied to catalysts during drying to maintainmaterial temperature near the final drying line out temperature for allbut about the first hour of drying when evaporation is rapid and thebatch cools. The resulting measured flow indices of 118 and 114 dg/min,respectively, show total drying times of 16 to 19 hours and drying lineout times of about 15 to 18 hours have no significant effect on catalystflow index response.

Examples 10 through 14

In Examples 10 through 14, DEAlE-reduced chromium oxide-based catalystswere prepared on a plant scale using activated C35300MSF support asdescribed above. Catalyst preparation conditions used are indicated inTable 1 (agitation rate during DEAlE addition and reaction, wt % Alloading, DEAlE addition time, DEAlE feed arrangement, and drying lineout temperature and time). Batch size for Comparative Example 10 wasabout 100% full where full refers to a batch size that just reaches thetop of the agitator impeller blades. Batch sizes for Examples 11 through14 were about 95% full.

TABLE 1 Catalyst Preparation Conditions for Examples 1-14 and Lab SlurryPolymerization Results for Examples 1-9 DEAlE Feed Arrangement InsertTube DEAlE Length Below Radial Drying Line Measured Catalyst Scale ofAgitation Addition Underside of Location Out Drying Line Flow IndexActivity catalyst rate Time wt % Al Top Head from Temperature Out TimeResponse (g PE/g Example preparation (rpm) (min) Loading (inches) Center(° C.) (hrs) (g/10 min) cat/1 hr) Comparative Pilot 37 39 1.57 No insert~90% 70.4 6.3 20  745 Ex. 1 tube Comparative Pilot 37 39 1.57 No insert~90% 70.4 6.3 35  976 Ex. 2 tube Comparative Pilot 37 39 1.58 No insert~90% 71.3 9.7 — — Ex. 3 tube Ex. 4 Pilot 30 40 1.54 0.5 ~83% 81.7 10.977 1449 Ex. 5 Pilot 30 40 1.58 0.5 ~83% 72.0 9.2 76 1555 Ex. 6 Pilot 3040 1.53 0.5 ~83% 61.0 8.3 101 1679 Ex. 7 Pilot 30 41 1.53 1 ~67% 71.07.1 104 1581 Ex. 8 Pilot 30 39 1.53 1 ~67% 63.2 15.3 118 1710 Ex. 9Pilot 30 38 1.57 1 ~67% 63.4 17.8 114 1627 Comparative Plant 30 37 1.35No insert ~54% 73.0 6.3 — — Ex. 10 tube Ex. 11 Plant 30 40 1.35 Noinsert ~54% 64.6 8.4 — — tube Ex. 12 Plant 30 40 1.29 No insert ~54%65.3 9.3 — — tube Ex. 13 Plant 30 39 1.33 2 ~74% 64.3 8.5 — — Ex. 14Plant 30 42 1.34 2 ~54% 62.9 8.4 — —

Examples 15 through 19

In Examples 15 through 19, DEAlE-reduced chromium oxide-based catalystswere prepared on a pilot scale using activated C35300MSF support asdescribed above and then tested for flow index response in a gas-phasefluidized bed polymerization reactor. Specifically, the catalystsprepared in Comparative Example 3 and in Examples 4 through 7 wereutilized in these polymerization examples. Catalyst preparationconditions used are indicated in Tables 1 and 2 (agitation rate duringDEAlE addition and reaction, wt % Al loading, DEAlE addition time, DEAlEfeed arrangement, and drying line out temperature and time).Polymerization results are shown in Table 2 below and in FIG. 5 above.

The results show that at an agitation rate within a narrow range, andwithin a narrow range of wt % Al loading, and within a narrow range ofDEAlE addition time, the measured flow index response increased when theDEAlE was fed with an insert tube to substantially prevent it fromrunning down the underside of the vessel head over to the vessel wall,and the measured flow index response increased further when the tube tipwas located further from the wall, which meant more towards the centerof the vessel.

Comparative Example 15 shows the relatively low measured flow index(4.43 dg/min) obtained for polymer from a gas-phase fluidized bed pilotplant polymerization with pilot-plant reduced catalyst, made without aninsert tube and with the DEAlE added about 90% of the distance radiallyfrom the vertical center line of the vessel, so at a position very nearthe wall. Examples 17 and 19 in comparison with Comparative Example 15show that when an insert tube of at least 0.5 inch protrusion below thetop head was used, at a location about 83% of the radial distance fromthe vertical centerline of the vessel, the measured flow index increasedsignificantly to 5.31 dg/min, and it increased further to 8.20 when aninsert with 1-inch protrusion was used at a location about 67% of theradial distance from the vertical centerline of the vessel. FIG. 5 abovedisplays this effect in a bar chart. The drying line out temperature was71 to 72° C. in these three examples. Examples 16 to 18 show that whendrying line out temperature was reduced from the region of 72 to 82° C.down to about 61° C., the measured flow index significantly increased,from the region of about 5.1 to 5.3 to about 7.6 dg/min. FIG. 7 abovedisplays this effect graphically. As shown by the examples above, it ispossible to tailor the flow index response of pilot-scale DEAlE-reducedactivated C35300MSF-based chromium oxide catalysts by varying the DEAlEfeed location radially, by using a DEAlE feed tube insert protrudingbelow the underside of the top head of the vessel, and/or by varying thecatalyst drying line out temperature (and time).

TABLE 2 Catalyst Information, Pilot Plant Reaction Conditions, andAverage Resin Properties for Examples 15-19 EXAMPLE Comparative 15 16 1718 19 Catalyst Info: From Example Number Comparative 3 4 5 6 7 ScaleReduced Pilot Pilot Pilot Pilot Pilot Support Type C35300MSF C35300MSFC35300MSF C35300MSF C35300MSF Cr, wt % 0.99 1.00 1.00 0.99 1.00 wt % AlLoading on Catalyst 1.58 1.54 1.58 1.53 1.53 DEAlE Add. Time (min) 39 4040 40 41 Agitation Speed (rpm) 37 30 30 30 30 DEAlE Tube Intrusion(inch) None 0.5 0.5 0.5 1 DEAlE Feed Radial from Center ~90% ~83% ~83%~83% ~67% Drying Line Out Temperature (° C.) 71.3 81.7 72.0 61.0 71.0Drying Line Out Time (hr) 9.7 10.9 9.2 8.3 7.1 Reaction Conditions: BedTemperature (° C.) 98.2 98.2 98.2 98.2 98.2 Reactor Pressure (psig) 346346 346 346 346 C2H4 Partial Pressure (psia) 200 200 200 200 200 H2/C2H4Ratio (molar) 0.039 0.040 0.040 0.040 0.040 C6H12/C2H4 Ratio (molar)0.0100 0.0100 0.0100 0.0100 0.0100 O2/C2H4 Ratio (ppbv) 25.1 24.9 25.025.2 25.6 Production Rate (lb/hr) 60.8 54.6 52.8 56.6 53.2 Bed Weight(lb) 128 116 119 118 118 Fluidized Bulk Density (lb/ft3) 16.1 14.6 14.615.0 14.7 Residence Time (hr) 2.1 2.1 2.2 2.1 2.2 STY (lb/h/ft3) 7.8 6.96.6 7.2 6.6 Average Resin Properties: MI(I2) (dg/min) — — 0.041 0.0640.061 FI(I21) (dg/min) 4.43 5.09 5.31 7.60 8.20 MFR (I21/I2) — — 122 103135 Density (g/cm3) 0.9374 0.9415 0.9421 0.9449 0.9446 Settled BulkDensity (lb/ft3) 24.7 22.8 23.2 23.1 23.1 Cr, ppmw 1.39 1.26 1.18 1.221.18 Catalyst Productivity (lb/lb) 7111 7908 8462 8131 8432 AverageParticle Size (in) 0.0437 0.0411 0.0428 0.0324 0.0370

Examples 20 through 24

In Examples 20 through 24, DEAlE-reduced chromium oxide-based catalystswere prepared on plant scale using activated C35300MSF support asdescribed above and were then tested for flow index response in apilot-scale gas-phase fluidized-bed reactor. Specifically, the catalystsprepared in Comparative Example 10 and Examples 11 through 14 wereutilized. Catalyst preparation conditions used are indicated in Tables 1and 3 (agitation rate during DEAlE addition and reaction, wt % Alloading, DEAlE addition time, DEAlE feed arrangement, and drying lineout temperature and time). Polymerization results are shown in Table 3.The polymerization conditions were held constant. The reactor operatedwell with no instances of resin agglomeration or disruption to thepolymerization process.

The results in Table 3 show that at an agitation rate within a narrowrange, and within a narrow range of wt % Al loading, and within a narrowrange of DEAlE addition time, the measured flow index response increasedwhen the DEAlE was fed with an insert tube to substantially prevent itfrom running down the underside of the vessel head over to the vesselwall, and the measured flow index response increased further when thetube tip was located further from the wall, which meant more towards thecenter of the vessel. The results in Table 3 further show that at agiven agitation rate, for catalysts with similar wt % Al loading, andwithin a narrow range of DEAlE addition time, the measured flow indexresponse increases with decreasing drying line out temperature.Comparative Example 20 shows that with no DEAlE feed insert, with DEAlEadded ˜54% of the radial distance from the vessel centerline to thewall, and at 73° C. drying line out temperature and about 6 hours dryingline out time, a relatively low flow index of 4.48 dg/min was obtained.

Examples 21 and 22 compared with Example 20 show with no DEAlE feedinsert and with DEAlE feed at the same radial location and at about 8 to9 hrs drying line-out time, that as the drying line out temperature wasdecreased from 73° C. to about 65° C. for plant reduced activatedC35300MSF catalyst, the measured flow index increased about 13% from4.48 to the range of 5.0 to 5.1 dg/min. It is believed this increase inflow index was due to the decrease in drying line-out temperature andnot due to shorter total drying time of 18 hours in Comparative Example20, nor due to shorter drying line out time. See Examples 8 and 9. InExample 23 with a DEAlE insert tube protruding 2 inches below theunderside of the top head and located about 74% of the radial distancefrom the vertical centerline of the vessel to the wall, and at about 64°C. drying line out temperature, the measured flow index of 5.19 dg/minonly slightly increased over Examples 21 and 22, but increasedsignificantly over Comparative Example 20. The location in Example 23closer to the vessel wall limited the improvement provided by the DEAlEfeed insert. In Example 24 with a DEAlE insert tube protruding 2 inchesbelow the underside of the top head and located about 54% of the radialdistance from the vertical centerline of the vessel to the wall, and atabout 63° C. drying line out temperature, the measured flow index of5.95 dg/min was increased about 33% over Comparative Example 20 with noinsert and higher drying line out temperature of 73° C. The measuredflow index in Example 24 was increased 17% above Examples 21 and 22 withno DEAlE feed insert, but with similar low drying line out temperatureof about 65° C. The measured flow index in Example 24 was increasedabout 15% above Example 23 in which the same length DEAlE feed insertwas used and about the same drying line-out temperature, but the DEAlEfeed location was significantly closer to the vessel wall.

TABLE 3 Catalyst Information, Pilot Plant Reaction Conditions, andAverage Resin Properties for Examples 20-24 EXAMPLE Comparative 20 21 2223 24 Catalyst Info: From Example Number Comparative 10 11 12 13 14Scale Reduced Plant Plant Plant Plant Plant Support Type C35300MSFC35300MSF C35300MSF C35300MSF C35300MSF Cr, wt % 0.92 0.93 0.92 0.930.92 wt % Al Loading on Catalyst 1.35 1.35 1.29 1.33 1.34 DEAlE Add.Time (min) 37 40 40 39 42 Agitation Speed (rpm) 30 30 30 30 30 DEAlETube Intrusion (inch) None None None 2 2 DEAlE Feed Radial from Center~54% ~54% ~54% ~74% ~54% Drying Line Out Temperature (° C.) 73.0 64.665.3 64.3 62.9 Drying Line Out Time (hr) 6.3 8.4 9.3 8.5 8.4 ReactionConditions: Bed Temperature (° C.) 98.2 98.2 98.2 98.2 98.2 ReactorPressure (psig) 346 346 346 346 346 C2H4 Partial Pressure (psia) 200 200200 200 200 H2/C2H4 Ratio (molar) 0.040 0.040 0.039 0.040 0.039C6H12/C2H4 Ratio (molar) 0.0100 0.0100 0.0100 0.0100 0.0101 O2/C2H4Ratio (ppbv) 25.1 25.1 25.1 24.6 25.0 Production Rate (lb/hr) 59.7 58.259.3 62.7 60.6 Bed Weight (lb) 132 133 134 135 135 Fluidized BulkDensity (lb/ft3) 16.3 16.5 16.7 17.2 17.0 Residence Time (hr) 2.2 2.32.2 2.2 2.2 STY (lb/hr/ft3) 7.4 7.2 7.4 8.0 7.6 Average ResinProperties: MI(I2) (dg/min) — — — — — FI(I21) (dg/min) 4.48 5.10 5.005.19 5.95 MFR (I21/I2) — — — — — Density (g/cm3) 0.9413 0.9420 0.94160.9435 0.9435 Settled Bulk Density (lb/ft3) 24.9 24.2 24.0 25.2 25.6 Cr,ppmw 0.92 1.05 1.33 1.22 1.25 Catalyst Productivity (lb/lb) 9957 88766917 7623 7360 Average Particle Size (in) 0.0397 0.0410 0.0416 0.03680.0369

These examples illustrate, among other things, for reduced chromiumoxide catalysts the surprising effect on flow index response of usingdiffering DEAlE feed arrangements and different DEAlE feed radiallocations from the vertical centerline of the vessel and differentdrying line-out temperatures and times in both a fluidized-bed gas phasepolymerization process and in a slurry polymerization process, forpolyethylene copolymers, which included ethylene units as well as othermonomeric units. These effects may be utilized to tailor the flow indexresponse of a catalyst so as to make target polymers with high, medium,or low flow indices under a variety of polymerization conditions.

As described above and illustrated in the Examples, the flow indexresponse of a chromium-based catalyst can be tailored by contacting thechromium-based catalyst with a reducing agent fed at a selected radiallocation from the vertical centerline of the vessel and with a feedinsert protruding below the underside of the vessel head, and optionallydrying at a drying line-out temperature of less than 68° C. The use ofthe chromium-based catalyst compositions described herein, wherein thecatalysts have a tailored or selected flow index response, provides acapacity for polymerization process flexibility, which has significantcommercial application in the polymerization of polyolefins.

Inline Reduction Examples

Gas phase fluid bed polymerizations were conducted in a similar manneras that employed in previous gas phase Examples. With respect to thecatalyst systems, comparative Examples 25 and 26 employ DEAlE reducedcatalyst prepared on a plant scale using activated C35300MSF support asdescribed above. Catalyst preparation conditions used are mostlyindicated in Table 4 and were very similar to those used in comparativeExample 10. DEAlE was added about 54% of the distance radially from thevertical center line of the vessel and no insert tube was used. Dryingline out temperature and time were 73.4° C. and 5.35 hrs. Batch size wasabout 99% full where full refers to a batch size that just reaches thetop of the agitator impeller blades.

Examples 27-30 use unreduced activated C35300MS chromium oxide catalystprepared as described earlier under General Catalyst Preparation. In allcases, the chromium oxide catalysts were activated at 600° C. in air. InExamples 27-30, the unreduced catalyst and DEAlE reducing agent are fedthrough a 100 ml Parr Series 4560 Mini Reactor bottom-port type vessel(Parr Instrument Company, Moline, Ill., USA), hereafter referred to asthe Parr Mixer at temperatures between 14 and 23° C. before addition tothe polymerization reactor. The chromium oxide catalyst is fed as 11.2wt % mineral oil slurry and the reducing agent is fed as a 0.20 wt %solution in isopentane. The air-driven stirrer near the bottom of theParr Mixer includes a four-blade turbine with no pitch on the blades(0.25 inch height, 0.75 inch diameter). The chromium oxide catalystslurry enters by a dip tube at a point just above the stirrer. Thereducing agent enters at the top of the Parr Mixer, and the mixedcontents exit at the bottom. An optional line for adding additionalisopentane to the Parr Mixer also enters at the top. The Parr Mixeroperates at a pressure higher than that of the polymerization reactor.The reduced catalyst is conveyed to the polymerization reactor with anauxiliary stream of carrier isopentane, with the possible addition of anitrogen carrier gas by a tee or Y-block at a location in the line nearwhere it enters the reactor. The catalyst enters the reactor fluid bedabout 1.5 to 2.0 ft above the distributor plate via a section ofstainless steel tubing that may extend inside typically about ¼ to ½ ofthe distance across the diameter of the pilot reactor straight-section.

In comparative Example 25 the catalyst is fed dry to the reactorproducing a polymer with a certain flow index and density. Incomparative Example 26, the reduced catalyst is fed to the reactor as an11.2 wt % slurry. It can be seen there is some loss in catalystproductivity and increase in polymer flow index value possibly due toimpurities in the oil slurry.

In Example 27, the reducing agent is fed to the mixer along with thechromium oxide catalyst at approximately the same ratio to chromium asthat found in the comparative examples. It can be seen that the polymerflow index and catalyst productivity increased significantly. ComparingExamples 26 with 27, the flow index response increased from about 10dg/min (batch reduced and dried isolated catalyst) to about 48 dg/min(inline reduction of the catalyst). Examples 28-30 show that polymerflow index can be controlled by varying the ratio of the reducing agentto chromium oxide catalyst. Significantly less reducing agent is neededto achieve the same flow index response as that obtained with mix tankreduced catalyst. In all inline reduction cases the polymer morphologyis maintained with no loss in polymer bulk density. Examples 28 and 29show that at a constant DEAlE feed ratio, reaction temperature andhydrogen to ethylene molar ratio can be employed to adjust polymer flowindex. The mixer average residence time listed in Table 4 may be labeledas the average contact residence time of the DEAlE with the catalyst inthe mixer. The Al Added wt % and DEAlE (added)/Cr mole ratio representthe DEAlE added in the inline reduction and are determined based on theinline DEAlE feed rate and the catalyst feed rate.

TABLE 4 Inline Reduction EXAMPLE Comparative 25 Comparative 26 27 28 2930 Catalyst Information: Scale Reduced Plant Plant Pilot Pilot PilotPilot Support Type C35300MSF C35300MSF C35300MS C35300MS C35300MSC35300MS Cr (wt %) 0.915 0.915   0.936   0.936   0.936   0.936 AlLoading on Catalyst (wt %) 1.325 1.325 None None None None DEAlE/Cr MoleRatio 2.79 2.79 0  0  0  0  DEAlE Add. Time (min) 38 38 — — — —Agitation Speed (rpm) 30 30 — — — Inline Reduction: Catalyst Feed DrySlurry Slurry Slurry Slurry Slurry Slurry Concentration (wt %) — 11.211.2 11.2 11.2 11.2 Catalyst Feed by Slurry (g/hr) — 5.34  4.70  4.81 4.81  4.92 Inline Reducing Agent None None 0.20 wt % 0.20 wt % 0.20 wt% 0.20 wt % DEAlE in DEAlE in DEAlE in DEAlE in Isopentane IsopentaneIsopentane Isopentane Inline Mixing — — Parr Mixer Parr Mixer Parr MixerParr Mixer Reducing Agent Feed (g/hr) — — 167   86   86   82   Al Addedto Catalyst (wt %) — —    1.43 *    0.72 *    0.72 *    0.68 * Al(Added)/Cr Mole Ratio — —    2.99 *    1.50 *    1.50 *    1.40 * MixerTemperature (° C.) — — 14-15 15   16-19 23-17 Mixer Stirrer Speed (rpm)— — 745   745   745   745   Mixer Avg. Residence Time (min) — — 19.118.8 18.5 18.6 Catalyst Nitrogen Carrier (lb/hr) 4.0 3.0  3.0  3.0  3.0 3.0 Catalyst Isopentane Carrier (lb/hr) — 3.0  2.6  2.6  2.6  2.6Injection Tube OD, inch 0.125 0.125   0.1875   0.1875   0.1875   0.1875Reaction Conditions: Bed Temperature (° C.) 106.0 106.0 106.0  106.0 102.0  102.9  Reactor Pressure (psig) 346 347 347   346   346   346  C2H4 Partial Pressure (psia) 200 200 200   200   200   200   H2/C2H4Ratio (molar) 0.099 0.099   0.100   0.099   0.050   0.043 C6H12/C2H4Ratio (molar) 0.00423 0.00456    0.00480    0.00480    0.00532   0.00548 O2/C2H4 Ratio (ppbv) 36.0 38.7 36.1 35.2 25.9 24.4 ProductionRate (lb/hr) 52.7 51.6 47.0 61.4 61.7 58.5 Bed Weight (lb) 124 124 124  123   121   123   Fluidized Bulk Density (lb/ft3) 15.1 15.7 15.7 15.615.1 15.8 Bed Height (ft) 8.6 8.3  8.3  8.3  8.4  8.2 Residence Time(hr) 2.35 2.40  2.63  2.01  1.97  2.11 STY (lb/hr/ft3) 6.4 6.5  6.0  7.8 7.7  7.5 Average Resin Properties: MI(I2) (dg/min) — —  0.58  0.12  0.089 — MI(I5) (dg/min) 0.36 0.47  2.87  0.66  0.51  0.17 FI(I21)(dg/min) 7.17 9.77 47.7 13.4 10.8  4.33 MFR (I21/I2) — — 83   111  122   — Density (g/cm3) 0.9476 0.9496   0.9586   0.9612   0.9513  0.9459 Settled Bulk Density (lb/ft3) 23.3 23.0 24.2 23.1 22.8 24.0Average Particle Size (in) 0.0382 0.0449   0.0320   0.0430   0.0383  0.0481 Fines < 120 Mesh Sieve (wt %) 1.29 0.81  2.83  2.03  2.05  1.61Catalyst Productivity (lb/lb) 8883 5209 5742    6440    6576   6078    * value calculated on inline DEAlE feed

Within each set, polymerization reactor temperature, hexene to ethylenegas phase molar ratios, and DEAlE level were varied for these catalystswith different flow index responses in order to make the desired polymerdensity and flow index. Other polymerization conditions were heldconstant within each set. Lower reactor temperature consistently leadsto lower flow index and lower melt index for a given DEAlE-reducedchromium catalyst.

Varying Batch Size Examples 31 through 35

In Examples 31 through 35, DEAlE-reduced chromium oxide-based catalystswere prepared on a plant scale using activated C35300MSF support asdescribed above. Catalyst preparation conditions used are indicated inTable 5 (batch size, agitation rate during DEAlE addition and reaction,wt % Al loading, DEAlE addition time, DEAlE feed arrangement, and dryingline out temperature and time). In Example 31 the batch size was about95% of full, such that the slurry surface was near to the top of thedouble helical ribbon impeller during the DEAlE addition. In Examples32, 33, 34 and 35, batch size was reduced to about 75% of full. This putthe slurry surface well below the top of the impeller. This is thoughtto have contributed to better mixing of the surface where DEAlE is addedthroughout the DEAlE addition step and so to better distribution ofDEAlE throughout the batch. In Examples 34 and 35 longer DEAlE additiontime of 62 minutes was utilized in combination with the smaller batchsize and the feed nozzle insert. In Example 35 higher drying line outtemperature was utilized.

TABLE 5 Catalyst Preparation Conditions for Examples 31-35 DEAlE FeedArrangement Insert Tube DEAlE Length Below Drying Line- Scale ofC35300MSF Agitation Addition Underside of Radial Out Drying Line-catalyst Charge rate Time wt % Al Top Head Location Temperature Out TimeExample preparation (lbs) (rpm) (min) Loading (inches) from Center (°C.) (hrs) Ex. 31 Plant 1904 30 41 1.53 2 ~54% 63.8 8.1 Ex. 32 Plant 154830 42 1.55 2 ~54% 63.6 5.75 Ex. 33 Plant 1540 30 41 1.59 No insert ~54%62.9 4.25 tube Ex. 34 Plant 1549 30 62 1.54 2 ~54% 62.1 5.0 Ex. 35 Plant1548 30 63 1.54 2 ~54% 70.1 5.97

Examples 36 through 40

In Examples 36 through 40, DEAlE-reduced chromium oxide-based catalystswere prepared on a plant scale using activated C35300MSF support asdescribed above and were then tested for flow index response in apilot-scale gas-phase fluidized-bed reactor. Specifically, the catalystsprepared in Examples 31 through 35 were utilized. Catalyst preparationconditions used are indicated in Table 5 (batch size, agitation rateduring DEAlE addition and reaction, wt % Al loading, DEAlE additiontime, DEAlE feed arrangement, and drying line out temperature and time).Polymerization results are shown in Table 6. The polymerizationconditions were held constant. The reactor operated well with noinstances of resin agglomeration or disruption to the polymerizationprocess.

In Table 6 Example 37 in comparison with Example 36 shows when an inserttube with 2-inch protrusion below the top head was used at a location54% of the radial distance from the vertical centerline of the vessel,the smaller batch size yielded a catalyst with 66% higher measured flowindex (8.75 dg/min vs. 5.27 dg/min respectively). In Example 38, noDEAlE feed tube insert was utilized in a small batch, yet Table 6 showsthis catalyst gave significantly higher flow index (7.46 dg/min) inExample 38 than Example 36 (5.27 dg/min) with catalyst made with thenormal larger batch size and a DEAlE feed nozzle insert. Only a smallportion of this 42% increase in flow index would be expected to be dueto the just slightly higher (4.2% relatively) wt % Al in Example 38 vs.Example 36. In Example 39 vs. Example 37 it can be seen how increasingthe DEAlE addition time from 42 minutes to 62 minutes further increasedflow index from 8.75 dg/min to 9.54 dg/min. In Example 40 vs. Example 39it can be seen how increasing the drying line out temperature from 62.1°C. to 70.1° C. decreased flow index from 9.54 dg/min to 7.26 dg/min.

The results in Table 6 show that at an agitation rate within a narrowrange, and within a narrow range of wt % Al loading, and within a narrowrange of DEAlE addition time, the measured flow index response increasedwhen the batch size was reduced such that the slurry surface was wellbelow the top of the impeller throughout the DEAlE addition.Furthermore, the combination of smaller batch size with an insert tubein the DEAlE addition nozzle gave a relatively high increase in flowindex response. Lengthening the DEAlE addition time from 42 to 62minutes gave the highest increase in flow index response in these tests.Raising the drying line out temperature reduced flow index response.

TABLE 6 Catalyst Information, Pilot Plant Reaction Conditions, andAverage Resin Properties for Examples 36-40 EXAMPLE 36 37 38 39 40Catalyst Info: From Example Number 31 32 33 34 35 Scale Reduced PlantPlant Plant Plant Plant Support Type C35300MSF C35300MSF C35300MSFC35300MSF C35300MSF Support Charged (lbs) 1904 1548 1540 1549 1548 Cr,wt % 0.91 0.84 0.83 0.88 0.86 wt % Al Loading on Catalyst 1.53 1.55 1.591.54 1.54 DEAlE Add. Time (min) 41 42 41 62 63 Agitation Speed (rpm) 3030 30 30 30 DEAlE Tube Intrusion (inch) 2 2 None 2 2 DEAlE Feed Radialfrom Center ~54% ~54% ~54% ~54% ~54% Drying Line Out Temperature (° C.)63.8 63.6 62.9 62.1 70.1 Drying Line Out Time (hr) 8.1 5.75 4.25 5.05.97 Reaction Conditions: Bed Temperature (° C.) 98.2 98.2 98.2 98.298.2 Reactor Pressure (psig) 341 343 343 343 348 C2H4 Partial Pressure(psia) 200 200 200 200 200 H2/C2H4 Ratio (molar) 0.039 0.040 0.040 0.0400.040 C6H12/C2H4 Ratio (molar) 0.0100 0.0100 0.0100 0.0100 0.0100O2/C2H4 Ratio (ppbv) 25.3 25.6 25.4 25.6 25.4 Production Rate (lb/hr)59.7 56.0 57.0 55.4 52.3 Bed Weight (lb) 134 126 126 125 124 FluidizedBulk Density (lb/ft3) 17.6 16.3 16.4 16.1 16.2 Residence Time (hr) 2.22.2 2.2 2.3 2.4 STY (lb/h/ft3) 7.9 7.3 7.5 7.1 6.8 Average ResinProperties: MI(I2) (dg/min) — — — — — FI(I21) (dg/min) 5.27 8.75 7.469.54 7.26 MFR (I21/I2) — — — — — Density (g/cm3) 0.9429 0.9459 0.94490.9472 0.9461 Settled Bulk Density (lb/ft3) 25.1 24.1 24.2 24.1 25.5 Cr,ppmw 1.30 1.27 1.26 1.24 1.33 Catalyst Productivity (lb/lb) 7014 65626582 7170 6481 Average Particle Size (in) 0.0382 0.0385 0.0372 0.03760.0365

1.-16. (canceled)
 17. A method of preparing a chromium-based catalyst for the production of polyolefin, the method comprising: contacting a chromium-based catalyst with a reducing agent in presence of a solvent in a mix vessel to produce a reduced chromium-based catalyst; evaporating the solvent at a drying temperature to dry the reduced chromium-based catalyst; and specifying the drying temperature to give a desired flow index response of the reduced chromium-based catalyst.
 18. The method of claim 17, wherein the drying temperature is less than 68° C.
 19. The method of claim 17, wherein the drying temperature is less than 76° C.
 20. The method of claim 17, wherein evaporating comprises increasing an operating temperature of the mix vessel from a reaction temperature to the drying temperature.
 21. The method of claim 17, wherein evaporating comprises increasing a jacket temperature of the mix vessel from a reaction temperature to the drying temperature.
 22. The method of claim 17, wherein evaporating comprises reducing an operating pressure of the mix vessel.
 23. The method of claim 17, comprising polymerizing an olefin into a polyolefin in presence of the reduced chromium-based catalyst in a polymerization reactor.
 24. The method of claim 17, wherein the chromium-based catalyst comprises an inorganic oxide support having a pore volume of about 0.5 to about 6.0 cubic centimeters (cm3)/gram (g) and a surface area of about 200 to about 600 square meters (m2)/g.
 25. A method comprising: preparing a chromium oxide catalyst for the polymerization of an olefin into a polyolefin, the preparing comprising: mixing the chromium oxide catalyst with a reducing agent in a solvent to give a reduced chromium oxide catalyst; removing solvent from the reduced chromium oxide catalyst at a specified temperature set point; and adjusting the specified temperature set point to give a desired flow index response of the reduced chromium oxide catalyst; and collecting the reduced chromium oxide catalyst for delivery to a polyolefin polymerization reactor.
 26. The method of claim 25, wherein the reducing agent comprises an alkyl aluminum alkoxide. 